CN112110800A - 3-aryl-2-propyne-1-alcohol derivative and preparation method thereof - Google Patents
3-aryl-2-propyne-1-alcohol derivative and preparation method thereof Download PDFInfo
- Publication number
- CN112110800A CN112110800A CN202011030136.9A CN202011030136A CN112110800A CN 112110800 A CN112110800 A CN 112110800A CN 202011030136 A CN202011030136 A CN 202011030136A CN 112110800 A CN112110800 A CN 112110800A
- Authority
- CN
- China
- Prior art keywords
- aryl
- propyn
- derivative
- mixed solution
- ethyl acetate
- 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.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/28—Alcohols containing only six-membered aromatic rings as cyclic part with unsaturation outside the aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/28—Alcohols containing only six-membered aromatic rings as cyclic part with unsaturation outside the aromatic rings
- C07C33/30—Alcohols containing only six-membered aromatic rings as cyclic part with unsaturation outside the aromatic rings monocyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/40—Halogenated unsaturated alcohols
- C07C33/46—Halogenated unsaturated alcohols containing only six-membered aromatic rings as cyclic parts
- C07C33/48—Halogenated unsaturated alcohols containing only six-membered aromatic rings as cyclic parts with unsaturation outside the aromatic rings
- C07C33/483—Monocyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
-
- 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
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/30—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
A 3-aryl-2-propinyl-1-alcohol derivative and a preparation method thereof, which belong to the field of organic synthesis, in particular to a 3-propanone derivativeAryl-2-propyn-1-ol derivative and its preparation method are disclosed. The invention aims to solve the problems of high energy consumption, high cost and environmental pollution caused by the conditions of high temperature, metal catalysis, strong alkali or low temperature and the like required for synthesizing the existing 3-aryl-2-propyne-1-alcohol derivatives. The structural formula of the 3-aryl-2-propyn-1-ol derivative is as follows:
the method comprises the following steps: firstly, sequentially adding an aryl acetylene compound, ammonium salt, alkali, water and an organic solvent into a three-neck flask, and electrolyzing at room temperature under the air atmosphere and under the stirring condition; secondly, extracting, and distilling under reduced pressure to remove the solvent to obtain a crude product; and thirdly, purifying the crude product by silica gel column chromatography to obtain the 3-aryl-2-propyn-1-ol derivative. The invention can obtain the 3-aryl-2-propyne-1-alcohol derivative.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a 3-aryl-2-propyne-1-alcohol derivative and a preparation method thereof.
Background
The 3-aryl-2-propyn-1-ol derivative is used as an important raw material or an intermediate in organic synthesis, has wide application, and is a useful building block in various types of organic synthesis, in particular to the building blocks of different heterocyclic frameworks (shown in the attached figure 1 of the specification) and complex compounds (shown in the attached figure 2 of the specification). For example, in the field of pesticides and medicines, which are widely used for synthesizing various bioactive and pharmaceutically active macromolecular substances, see the attached figure 3 of the specification, substance 1 is an analgesic; substance 2 is a natural molecule, imperatorin, with biological activity; substance 3 is a protein kinase inhibitor intended for the treatment of cancer, diabetes and alzheimer's disease. Therefore, the synthesis of the 3-aryl-2-propyn-1-ol derivatives has important significance.
3-aryl-2-propyn-1-ol derivatives are important building blocks in biologically active compounds, and therefore, many synthetic methods for preparing them have been developed, mainly the following 4 types of synthetic methods: (1) the traditional synthetic methods mainly use strong base such as alkyl lithium, dialkyl zinc or organic magnesium reagent to activate terminal alkyne, therefore, the substrate range of these methods is very narrow, and low temperature condition of minus 78 ℃ is required; (2) aryl substituted propargyl alcohol is synthesized by using aryl halide and propargyl alcohol derivative, but is only used under laboratory conditions, because commercial terminal propargyl alcohol derivative is not many, the range of substrate is not wide, and the reaction needs noble metal Pd as catalyst and is expensive; (3) under mild conditions, alkynyl silane and silver compounds are used as alkynyl sources to react with aldehyde, but reagents must be prepared, so that one-step reaction is changed into more laborious two-step reaction, reaction steps are increased, and the green chemical and atom economy related requirements are not met to a certain extent; (4) copper catalyzed paraformaldehyde and terminal alkyne synthesis schemes are of great interest, however, it still requires harsh reaction conditions, such as strong bases and high temperatures. In summary, the existing synthesis method of the 3-aryl-2-propyn-1-ol derivative is mostly carried out under the metal catalysis condition, the reaction condition is harsh, and strong alkali, high temperature (100 ℃), low temperature minus 78 ℃ and other conditions are required. Therefore, a method which is green, efficient, mild in condition, simple in method, convenient to operate and high in yield is sought, and the problem to be solved is urgently solved for synthesizing the 3-aryl-2-propyn-1-ol derivative.
From the viewpoint of the source of the raw materials, conventionally, various sources of formaldehyde such as paraformaldehyde, trioxane, an aqueous formaldehyde solution (formalin), or gaseous formaldehyde in the form of a monomer. However, their use has several disadvantages: the reactivity of paraformaldehyde and trioxane is relatively low; paraformaldehyde has low solubility in an organic solvent, so that industrial scale reaction is hindered, and the method is not suitable for large-scale production; formalin is not suitable for reacting with nucleophiles that are easily protonated; the gaseous formaldehyde in the form of a monomer is a highly toxic gas. Therefore, the search for a simple, safe and versatile formaldehyde source is also a problem to be solved.
Disclosure of Invention
The invention aims to solve the problems of high energy consumption, high cost and environmental pollution caused by the conditions of high temperature, metal catalysis, strong alkali or low temperature and the like required for synthesizing the existing 3-aryl-2-propyn-1-ol derivative, and provides a 3-aryl-2-propyn-1-ol derivative and a preparation method thereof.
The structural formula of the 3-aryl-2-propyn-1-ol derivative is as follows:
wherein Ar is pyridine, thiophene, naphthalene or
A preparation method of 3-aryl-2-propyn-1-ol derivatives comprises the following steps:
firstly, sequentially adding an aryl acetylene compound, ammonium salt, alkali, water and an organic solvent into a three-neck flask, then installing two platinum plate electrodes in the three-neck flask, connecting the two platinum plate electrodes with a power supply, and electrolyzing for 1-3 hours at room temperature in an air atmosphere under the stirring condition to obtain a reaction mixture;
secondly, pouring the reaction mixture into saline water, extracting for 3 times by using ethyl acetate, and combining organic layers; reuse of anhydrous Na2SO4Drying the combined organic layers, and finally carrying out reduced pressure distillation to remove the solvent to obtain a crude product;
and thirdly, purifying the crude product by silica gel column chromatography, wherein the eluent is a mixed solution of ethyl acetate/petroleum ether to obtain the 3-aryl-2-propyn-1-ol derivative.
The invention has the beneficial effects that:
the invention provides a 3-aryl-2-propyne-1-alcohol derivative, which has potential biological activity and great research value; the derivative provided by the invention has higher research value, and can be used for screening a drug lead compound and used by scientific research units for biological activity test research and the like; the invention can also be used as a raw material for synthesizing other derivatives containing 3-aryl-2-propyn-1-ol;
the invention provides a simple one-step method for synthesizing the 3-aryl-2-propyne-1-alcohol derivative, which solves the problems of high energy consumption, high cost and environmental pollution caused by the conditions of high temperature, metal catalysis, strong alkali or low temperature and the like required in the synthesis of the existing 3-aryl-2-propyne-1-alcohol derivative, seeks a route for synthesizing the 3-aryl-2-propyne-1-alcohol derivative with green, high efficiency, mild conditions (room temperature), simple method, convenient operation and high yield, and lays a certain foundation for the industrial development of the 3-aryl-2-propyne-1-alcohol derivative;
the invention provides a simple, safe and widely-used method for generating formaldehyde in situ in an organic solvent, and the method avoids the use of gaseous formaldehyde. The aryl trimethyl ammonium triflate used in the invention can generate formaldehyde in situ, is a first report, has innovation, and is a very useful and universal synthetic method of 3-aryl-2-propyne-1-alcohol derivatives.
Drawings
FIG. 1 is a schematic diagram of different heterocyclic skeletons that can be constructed by 3-aryl-2-propyn-1-ol derivatives;
FIG. 2 is a schematic diagram of different complex compounds that can be constructed by 3-aryl-2-propyn-1-ol derivatives;
FIG. 3 shows various bioactive and pharmaceutically active macromolecular substances synthesized using 3-aryl-2-propyn-1-ol derivatives, substance 1 being an analgesic, substance 2 being a natural molecule, limonene, substance 3 being a protein kinase inhibitor;
FIG. 4 shows the 3-aryl-2-propyn-1-ol derivatives obtained in example 11H NMR spectrum.
FIG. 5 shows the 3-aryl-2-propyn-1-ol derivatives obtained in example 113C NMR spectrum.
Detailed Description
In order to make the technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The first embodiment is as follows: the structural formula of the 3-aryl-2-propyn-1-ol derivative is as follows:
wherein Ar is pyridine, thiophene, naphthalene or
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: said
Wherein R is alkoxy, alkyl, halogen or phenyl. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the preparation method of the 3-aryl-2-propyn-1-ol derivative of the embodiment is completed by the following steps:
firstly, sequentially adding an aryl acetylene compound, ammonium salt, alkali, water and an organic solvent into a three-neck flask, then installing two platinum plate electrodes in the three-neck flask, connecting the two platinum plate electrodes with a power supply, and electrolyzing for 1-3 hours at room temperature in an air atmosphere under the stirring condition to obtain a reaction mixture;
secondly, pouring the reaction mixture into saline water, extracting for 3 times by using ethyl acetate, and combining organic layers; reuse of anhydrous Na2SO4Drying the combined organic layers, and finally carrying out reduced pressure distillation to remove the solvent to obtain a crude product;
and thirdly, purifying the crude product by silica gel column chromatography, wherein the eluent is a mixed solution of ethyl acetate/petroleum ether to obtain the 3-aryl-2-propyn-1-ol derivative.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the structural formula of the aryl acetylene compound in the step one is as follows:
wherein Ar is pyridine, thiophene, naphthalene or
The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: said
Wherein R is alkoxy, alkyl, halogen or phenyl. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: the current of the electrolysis in the step one is constant current, and the numerical value is 10 mA-20 mA; the molar ratio of the aryl acetylene compounds, the ammonium salt, the water and the alkali in the step one is 1:1.8:7: 2; the molar ratio of the aryl acetylene compounds to the organic solvent in the step one is 1mmol:20 mL. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the two platinum plate electrodes in the step one are both 10 multiplied by 0.1mm in size, and the distance between the two platinum plate electrodes is 2 cm; the alkali in the step one is sodium carbonate, sodium hydroxide or sodium ethoxide; the organic solvent in the first step is anhydrous N, N-dimethylformamide or anhydrous N, N-dimethylacetamide. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the ammonium salt in the step one is N, N, N-trimethylbenzene ammonium triflate or N, N, N-trimethylbenzyl ammonium triflate; the structural formula of the N, N, N-trimethylbenzene ammonium trifluoromethanesulfonate is shown in the specification
The structural formula of the N, N, N-trimethylbenzylammonium triflate is shown in the specification
The preparation method of the N, N, N-trimethylbenzene ammonium trifluoromethyl sulfonate comprises the following steps: first, 10mmol of N, N-dimethylaniline and 10mL of CH were added sequentially to a dry round-bottomed flask equipped with a magnetic stirrer2Cl2Then, dropwise adding 11mmol of trifluoromethyl methyl sulfonate at room temperature to obtain a mixed solution; stirring the mixed solution at room temperature for 4h to obtain a reaction product, and concentrating and removing the reaction product by using a rotary evaporatorRemoving CH in reaction product2Cl2Obtaining a solid substance; washing with methyl tert-butyl ether for 3 times, and vacuum drying to obtain N, N, N-trimethylbenzene ammonium triflate; the preparation method of the N, N, N-trimethylbenzylammonium triflate is as follows: first, 10mmol of N, N-dimethylbenzylamine and 10mL of CH were sequentially added to a dry round-bottomed flask equipped with a magnetic stirrer2Cl2Obtaining a mixed solution; placing the mixed solution at 0 ℃, dropwise adding 11mmol of methyl trifluoromethanesulfonate into the mixed solution at 0 ℃, and stirring at room temperature for 2 hours to obtain a reaction product; removing CH in the reaction product by concentration of a rotary evaporator2Cl2Obtaining a solid substance; washing 3 times with methyl tert-butyl ether, and finally vacuum drying to obtain the N, N, N-trimethylbenzylammonium triflate. The other steps are the same as those in the first to seventh embodiments.
The reaction formula of the N, N-trimethylanilinium triflate in this embodiment is:
the reaction formula of the N, N-trimethylbenzylammonium triflate in this embodiment is:
the specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the brine in the step two is saturated brine; the power supply in the second step is a potentiostat, which is purchased from Shanghai Xinrui instruments and meters Limited, potentiostat model: DJS-292B (C) potentiostat; and the temperature of the reduced pressure distillation in the step two is 35 ℃, and the pressure is 0.1 MPa. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is as follows: the volume ratio of the reaction mixture to the brine in the second step is 4: 15; the volume ratio of the ethyl acetate to the petroleum ether in the ethyl acetate/petroleum ether mixed solution in the third step is 1 (2-5). The other steps are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: the preparation method of the 3-aryl-2-propyn-1-ol derivative comprises the following steps:
firstly, sequentially adding 0.2mmol of 3-ethynylanisole, 0.36mmol of N, N, N-trimethylbenzene ammonium triflate, 0.4mmol of sodium carbonate, 1.4mmol of water and 4mL of N, N-dimethylacetamide into a 25mL three-necked flask, then installing two platinum plate electrodes in the three-necked flask, connecting the two platinum plate electrodes with a power supply, and electrolyzing for 2 hours at room temperature in an air atmosphere under stirring conditions to obtain a reaction mixture;
the current of the electrolysis in the step one is 15mA constant current;
the two platinum plate electrodes in the step one are both 10 multiplied by 0.1mm in size, and the distance between the two platinum plate electrodes is 2 cm;
secondly, pouring the reaction mixture into 15mL of saline, extracting for 3 times by using ethyl acetate, and combining organic layers; reuse of anhydrous Na2SO4Drying the combined organic layers, and finally carrying out reduced pressure distillation to remove the solvent to obtain a crude product;
the brine in the step two is saturated brine;
the power supply in the second step is a potentiostat;
the temperature of the reduced pressure distillation in the step two is 35 ℃, and the pressure is 0.1 MPa;
and thirdly, purifying the crude product by silica gel column chromatography, wherein the eluent is a mixed solution of ethyl acetate/petroleum ether to obtain the 3-aryl-2-propyn-1-ol derivative.
The volume ratio of the ethyl acetate to the petroleum ether in the mixed solution of the ethyl acetate and the petroleum ether in the third step is 1: 5.
The reaction equation for example 1 is:
the 3-aryl-2-propyn-1-ol derivative prepared in example 1 had a purity of 99% and a yield of 72.0%, and its 1H NMR and 13C NMR charts are shown in fig. 4 and 5 in appendix 1, respectively.
FIG. 4 shows the 3-aryl-2-propyn-1-ol derivatives obtained in example 11H NMR spectrum.
FIG. 5 shows the 3-aryl-2-propyn-1-ol derivatives obtained in example 113C NMR spectrum.
The nuclear magnetic data analysis was:1H NMR(400MHz,Chloroform-d)7.21(t,J＝8.0Hz,1H),7.03(d,J＝7.6Hz,1H),6.97(s,1H),6.88(dd,J＝8.3,2.5Hz,1H),4.49(s,2H),3.79(s,3H),1.99(br,1H)。13C NMR(101MHz,Chloroform-d)159.2,129.4,124.2,123.5,116.5,115.0,87.0,85.6,55.2,51.6。
example 2: the preparation method of the 3-aryl-2-propyn-1-ol derivative comprises the following steps:
firstly, sequentially adding 0.2mmol of 4-tert-butylphenyl acetylene, 0.36mmol of N, N, N-trimethyl anilinium triflate, 0.4mmol of sodium carbonate, 1.4mmol of water and 4mL of N, N-dimethylacetamide into a 25mL three-necked flask, then installing two platinum plate electrodes in the three-necked flask, connecting the two platinum plate electrodes with a power supply, and electrolyzing for 2 hours at room temperature in an air atmosphere under stirring conditions to obtain a reaction mixture;
the current of the electrolysis in the step one is 15mA constant current;
the two platinum plate electrodes in the step one are both 10 multiplied by 0.1mm in size, and the distance between the two platinum plate electrodes is 2 cm;
secondly, pouring the reaction mixture into 15mL of saline, extracting for 3 times by using ethyl acetate, and combining organic layers; reuse of anhydrous Na2SO4Drying the combined organic layers, and finally carrying out reduced pressure distillation to remove the solvent to obtain a crude product;
the brine in the step two is saturated brine;
the power supply in the second step is a potentiostat;
the temperature of the reduced pressure distillation in the step two is 35 ℃, and the pressure is 0.1 MPa;
and thirdly, purifying the crude product by silica gel column chromatography, wherein the eluent is a mixed solution of ethyl acetate/petroleum ether to obtain the 3-aryl-2-propyn-1-ol derivative.
The volume ratio of the ethyl acetate to the petroleum ether in the mixed solution of the ethyl acetate and the petroleum ether in the third step is 1: 5.
The reaction equation for example 2 is:
the 3-aryl-2-propyn-1-ol derivative prepared in example 2 had a purity of 99% and a yield of 72.6%, and the nuclear magnetic data analysis showed:1H NMR(400MHz,Chloroform-d)7.46–7.34(m,4H),4.53(s,2H),1.86(br,1H),1.35(s,9H)。13C NMR(101MHz,Chloroform-d)151.7,131.4,125.3,119.4,86.5,85.8,51.7,34.7,31.1。
example 3: the preparation method of the 3-aryl-2-propyn-1-ol derivative comprises the following steps:
firstly, sequentially adding 0.2mmol of 1-ethynyl-2-fluorobenzene, 0.36mmol of N, N, N-trimethylbenzene ammonium triflate, 0.4mmol of sodium carbonate, 1.4mmol of water and 4mL of N, N-dimethylacetamide into a 25mL three-necked flask, then installing two platinum plate electrodes in the three-necked flask, connecting the two platinum plate electrodes with a power supply, and electrolyzing for 2 hours at room temperature in an air atmosphere under stirring conditions to obtain a reaction mixture;
the current of the electrolysis in the step one is 15mA constant current;
the two platinum plate electrodes in the step one are both 10 multiplied by 0.1mm in size, and the distance between the two platinum plate electrodes is 2 cm;
secondly, pouring the reaction mixture into 15mL of saline, extracting for 3 times by using ethyl acetate, and combining organic layers; reuse of anhydrous Na2SO4Drying the combined organic layers, and finally carrying out reduced pressure distillation to remove the solvent to obtain a crude product;
the brine in the step two is saturated brine;
the power supply in the second step is a potentiostat;
the temperature of the reduced pressure distillation in the step two is 35 ℃, and the pressure is 0.1 MPa;
and thirdly, purifying the crude product by silica gel column chromatography, wherein the eluent is a mixed solution of ethyl acetate/petroleum ether to obtain the 3-aryl-2-propyn-1-ol derivative.
The volume ratio of the ethyl acetate to the petroleum ether in the mixed solution of the ethyl acetate and the petroleum ether in the third step is 1: 5.
The reaction equation for example 3 is:
the 3-aryl-2-propyn-1-ol derivative prepared in example 3 had a purity of 99% and a yield of 94.9%, and the nuclear magnetic data analysis showed:1H NMR(400MHz,Chloroform-d)7.43(td,J＝7.4,1.8Hz,1H),7.35–7.27(m,1H),7.13–7.02(m,2H),4.53(s,2H),1.96(br,1H).
13C NMR(101MHz,Chloroform-d)162.8(d,J＝251.5Hz),133.6,130.2(d,J＝8.0Hz),123.9(d,J＝3.7Hz),115.5(d,J＝20.9Hz),111.1(d,J＝15.6Hz),92.4(d,J＝3.3Hz),79.0,51.6.
example 4: the preparation method of the 3-aryl-2-propyn-1-ol derivative comprises the following steps:
firstly, sequentially adding 0.2mmol of 1-chloro-2-ethynylbenzene, 0.36mmol of N, N, N-trimethylbenzene ammonium triflate, 0.4mmol of sodium carbonate, 1.4mmol of water and 4mL of N, N-dimethylacetamide into a 25mL three-necked flask, then installing two platinum plate electrodes in the three-necked flask, connecting the two platinum plate electrodes with a power supply, and electrolyzing for 2 hours at room temperature in an air atmosphere and under stirring conditions to obtain a reaction mixture;
the current of the electrolysis in the step one is 15mA constant current;
the two platinum plate electrodes in the step one are both 10 multiplied by 0.1mm in size, and the distance between the two platinum plate electrodes is 2 cm;
secondly, pouring the reaction mixture into 15mL of saline, extracting for 3 times by using ethyl acetate, and combining organic layers; reuse of anhydrous Na2SO4Drying the combined organic layers, and finally carrying out reduced pressure distillation to remove the solvent to obtain a crude product;
the brine in the step two is saturated brine;
the power supply in the second step is a potentiostat;
the temperature of the reduced pressure distillation in the step two is 35 ℃, and the pressure is 0.1 MPa;
and thirdly, purifying the crude product by silica gel column chromatography, wherein the eluent is a mixed solution of ethyl acetate/petroleum ether to obtain the 3-aryl-2-propyn-1-ol derivative.
The volume ratio of the ethyl acetate to the petroleum ether in the mixed solution of the ethyl acetate and the petroleum ether in the third step is 1: 5.
The reaction equation for example 4 is:
the 3-aryl-2-propyn-1-ol derivative prepared in example 4 had a purity of 99% and a yield of 95.4%, and the nuclear magnetic data analysis showed:1H NMR(400MHz,Chloroform-d)7.47(dd,J＝7.5,1.9Hz,1H),7.39(dd,J＝7.9,1.3Hz,1H),7.23(dtd,J＝19.9,7.5,1.6Hz,2H),4.56(s,2H),2.21(br,1H)。13C NMR(101MHz,Chloroform-d)135.8,133.5,129.5,129.2,126.4,122.4,92.4,82.3,51.6。
example 5: the preparation method of the 3-aryl-2-propyn-1-ol derivative comprises the following steps:
firstly, sequentially adding 0.2mmol of 1-ethynyl-4-methylbenzene, 0.36mmol of N, N, N-trimethylbenzene ammonium triflate, 0.4mmol of sodium carbonate, 1.4mmol of water and 4mL of N, N-dimethylacetamide into a 25mL three-necked flask, then installing two platinum plate electrodes in the three-necked flask, connecting the two platinum plate electrodes with a power supply, and electrolyzing for 2 hours at room temperature in an air atmosphere and under stirring conditions to obtain a reaction mixture;
the current of the electrolysis in the step one is 15mA constant current;
the two platinum plate electrodes in the step one are both 10 multiplied by 0.1mm in size, and the distance between the two platinum plate electrodes is 2 cm;
secondly, pouring the reaction mixture into 15mL of saline, extracting for 3 times by using ethyl acetate, and combining organic layers; reuse of anhydrous Na2SO4Drying the combined organic layers, and finally carrying out reduced pressure distillation to remove the solvent to obtain a crude product;
the brine in the step two is saturated brine;
the power supply in the second step is a potentiostat;
the temperature of the reduced pressure distillation in the step two is 35 ℃, and the pressure is 0.1 MPa;
and thirdly, purifying the crude product by silica gel column chromatography, wherein the eluent is a mixed solution of ethyl acetate/petroleum ether to obtain the 3-aryl-2-propyn-1-ol derivative.
The volume ratio of the ethyl acetate to the petroleum ether in the mixed solution of the ethyl acetate and the petroleum ether in the third step is 1: 5.
The reaction equation for example 5 is:
the 3-aryl-2-propyn-1-ol derivative prepared in example 5 had a purity of 99% and a yield of 79.1%, and the nuclear magnetic data analysis showed:1H NMR(600MHz,Chloroform-d)7.33(d,J＝7.9Hz,2H),7.11(d,J＝7.8Hz,2H),4.49(s,2H),2.34(s,3H),1.98(br,1H)。13C NMR(151MHz,Chloroform-d)138.59,131.53,129.03,119.38,86.50,85.75,51.62,21.43。
example 6: the preparation method of the 3-aryl-2-propyn-1-ol derivative comprises the following steps:
firstly, sequentially adding 0.2mmol of 3-ethynylpyridine, 0.36mmol of N, N, N-trimethylbenzene ammonium triflate, 0.4mmol of sodium carbonate, 1.4mmol of water and 4mL of N, N-dimethylacetamide into a 25mL three-neck flask, then installing two platinum plate electrodes in the three-neck flask, connecting the two platinum plate electrodes with a power supply, and electrolyzing for 2 hours at room temperature in an air atmosphere under stirring conditions to obtain a reaction mixture;
the current of the electrolysis in the step one is 15mA constant current;
the two platinum plate electrodes in the step one are both 10 multiplied by 0.1mm in size, and the distance between the two platinum plate electrodes is 2 cm;
secondly, pouring the reaction mixture into 15mL of saline, extracting for 3 times by using ethyl acetate, and combining organic layers; reuse of anhydrous Na2SO4Drying the combined organic layers, and finally carrying out reduced pressure distillation to remove the solvent to obtain a crude product;
the brine in the step two is saturated brine;
the power supply in the second step is a potentiostat;
the temperature of the reduced pressure distillation in the step two is 35 ℃, and the pressure is 0.1 MPa;
and thirdly, purifying the crude product by silica gel column chromatography, wherein the eluent is a mixed solution of ethyl acetate/petroleum ether to obtain the 3-aryl-2-propyn-1-ol derivative.
The volume ratio of the ethyl acetate to the petroleum ether in the mixed solution of the ethyl acetate and the petroleum ether in the third step is 1: 5.
The reaction equation for example 6 is:
the 3-aryl-2-propyn-1-ol derivative prepared in example 6 had a purity of 99% and a yield of 83.6%, and its nuclear magnetic data analysis showed:1H NMR(400MHz,Chloroform-d)8.78(dd,J＝2.2,0.9Hz,1H),8.51(dd,J＝5.0,1.7Hz,1H),7.74(dt,J＝7.9,1.9Hz,1H),7.30–7.26(m,1H),4.72(br,1H),4.51(s,2H)。13C NMR(101MHz,Chloroform-d)152.1,148.3,139.1,123.4,120.3,92.2,81.5,50.9。
example 7: the preparation method of the 3-aryl-2-propyn-1-ol derivative comprises the following steps:
firstly, sequentially adding 0.2mmol of 3-ethynylthiophene, 0.36mmol of N, N, N-trimethylbenzene ammonium triflate, 0.4mmol of sodium carbonate, 1.4mmol of water and 4mL of N, N-dimethylacetamide into a 25mL three-neck flask, then installing two platinum plate electrodes in the three-neck flask, connecting the two platinum plate electrodes with a power supply, and electrolyzing for 2 hours at room temperature in an air atmosphere under stirring conditions to obtain a reaction mixture;
the current of the electrolysis in the step one is 15mA constant current;
the two platinum plate electrodes in the step one are both 10 multiplied by 0.1mm in size, and the distance between the two platinum plate electrodes is 2 cm;
secondly, pouring the reaction mixture into 15mL of saline, extracting for 3 times by using ethyl acetate, and combining organic layers; reuse of anhydrous Na2SO4Drying the combined organic layers, and finally carrying out reduced pressure distillation to remove the solvent to obtain a crude product;
the brine in the step two is saturated brine;
the power supply in the second step is a potentiostat;
the temperature of the reduced pressure distillation in the step two is 35 ℃, and the pressure is 0.1 MPa;
and thirdly, purifying the crude product by silica gel column chromatography, wherein the eluent is a mixed solution of ethyl acetate/petroleum ether to obtain the 3-aryl-2-propyn-1-ol derivative.
The volume ratio of the ethyl acetate to the petroleum ether in the mixed solution of the ethyl acetate and the petroleum ether in the third step is 1: 5.
The reaction equation for example 7 is:
the 3-aryl-2-propyn-1-ol derivative prepared in example 7 had a purity of 99% and a yield of 74.3%, and its nuclear magnetic data analysis showed:1H NMR(400MHz,Chloroform-d)7.45(dd,J＝3.0,1.1Hz,1H),7.25(dd,J＝5.0,3.0Hz,1H),7.10(dd,J＝5.0,1.1Hz,1H),4.47(s,2H),2.06(br,1H)。13C NMR(101MHz,Chloroform-d)129.9,129.2,125.5,121.6,86.9,80.9,51.6.。
example 8: the preparation method of the 3-aryl-2-propyn-1-ol derivative comprises the following steps:
firstly, sequentially adding 0.2mmol of 2-ethynylnaphthalene, 0.36mmol of N, N, N-trimethylbenzene ammonium triflate, 0.4mmol of sodium carbonate, 1.4mmol of water and 4mL of N, N-dimethylacetamide into a 25mL three-necked flask, then installing two platinum plate electrodes in the three-necked flask, connecting the two platinum plate electrodes with a power supply, and electrolyzing for 2 hours at room temperature in an air atmosphere under stirring conditions to obtain a reaction mixture;
the current of the electrolysis in the step one is 15mA constant current;
the two platinum plate electrodes in the step one are both 10 multiplied by 0.1mm in size, and the distance between the two platinum plate electrodes is 2 cm;
secondly, pouring the reaction mixture into 15mL of saline, extracting for 3 times by using ethyl acetate, and combining organic layers; reuse of anhydrous Na2SO4Drying the combined organic layers, and finally carrying out reduced pressure distillation to remove the solvent to obtain a crude product;
the brine in the step two is saturated brine;
the power supply in the second step is a potentiostat;
the temperature of the reduced pressure distillation in the step two is 35 ℃, and the pressure is 0.1 MPa;
and thirdly, purifying the crude product by silica gel column chromatography, wherein the eluent is a mixed solution of ethyl acetate/petroleum ether to obtain the 3-aryl-2-propyn-1-ol derivative.
The volume ratio of the ethyl acetate to the petroleum ether in the mixed solution of the ethyl acetate and the petroleum ether in the third step is 1: 5.
The reaction equation for example 8 is:
the 3-aryl-2-propyn-1-ol derivative prepared in example 8 had a purity of 99% and a yield of 53.2%, and its nuclear magnetic data analysis showed: 1H NMR (400MHz, Chloroform-d) 8.01-7.93 (m,1H), 7.83-7.75 (m,3H), 7.53-7.45 (m,3H),4.56(s,2H),2.06(br, 1H).13C NMR(101MHz,Chloroform-d)132.9,131.8,128.4,128.1,127.8,126.9,126.6,119.9,87.6,86.1,51.8。
Example 9: the preparation method of the 3-aryl-2-propyn-1-ol derivative comprises the following steps:
firstly, sequentially adding 0.2mmol of 4-acetylene biphenyl, 0.36mmol of N, N, N-trimethyl benzene ammonium trifluoromethyl sulfonate, 0.4mmol of sodium carbonate, 1.4mmol of water and 4mL of N, N-dimethyl acetamide into a 25mL three-neck flask, then installing two platinum plate electrodes in the three-neck flask, connecting the two platinum plate electrodes with a power supply, and electrolyzing for 2 hours at room temperature in an air atmosphere under stirring conditions to obtain a reaction mixture;
the current of the electrolysis in the step one is 15mA constant current;
the two platinum plate electrodes in the step one are both 10 multiplied by 0.1mm in size, and the distance between the two platinum plate electrodes is 2 cm;
secondly, pouring the reaction mixture into 15mL of saline, extracting for 3 times by using ethyl acetate, and combining organic layers; reuse of anhydrous Na2SO4Drying the combined organic layers, and finally carrying out reduced pressure distillation to remove the solvent to obtain a crude product;
the brine in the step two is saturated brine;
the power supply in the second step is a potentiostat;
the temperature of the reduced pressure distillation in the step two is 35 ℃, and the pressure is 0.1 MPa;
and thirdly, purifying the crude product by silica gel column chromatography, wherein the eluent is a mixed solution of ethyl acetate/petroleum ether to obtain the 3-aryl-2-propyn-1-ol derivative.
The volume ratio of the ethyl acetate to the petroleum ether in the mixed solution of the ethyl acetate and the petroleum ether in the third step is 1: 5.
The reaction equation for example 9 is:
the 3-aryl-2-propyn-1-ol derivative prepared in example 9 had a purity of 99% and a yield of 64.9%, and its nuclear magnetic data analysis showed:1H NMR(400MHz,Chloroform-d)7.61–7.57(m,2H),7.57–7.49(m,4H),7.48–7.42(m,2H),7.39–7.34(m,1H),4.53(s,2H),1.98(br,1H)。13C NMR(101MHz,Chloroform-d)141.3,140.3,132.2,128.9,127.8,127.1,121.5,87.9,85.7,51.8。
the above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (10)
1. A3-aryl-2-propyn-1-ol derivative is characterized in that the structural formula of the 3-aryl-2-propyn-1-ol derivative is as follows:
wherein Ar is pyridine, thiophene, naphthalene or
2. A 3-aryl-2-propyn-1-ol derivative according to claim 1, wherein the derivative is
Wherein R is alkoxy, alkyl, halogen or phenyl.
3. The process for producing a 3-aryl-2-propyn-1-ol derivative according to claim 1, wherein the process for producing a 3-aryl-2-propyn-1-ol derivative comprises the steps of:
firstly, sequentially adding an aryl acetylene compound, ammonium salt, alkali, water and an organic solvent into a three-neck flask, then installing two platinum plate electrodes in the three-neck flask, connecting the two platinum plate electrodes with a power supply, and electrolyzing for 1-3 hours at room temperature in an air atmosphere under the stirring condition to obtain a reaction mixture;
secondly, pouring the reaction mixture into saline water, extracting for 3 times by using ethyl acetate, and combining organic layers; reuse of anhydrous Na2SO4Drying the combined organic layers, and finally carrying out reduced pressure distillation to remove the solvent to obtain a crude product;
and thirdly, purifying the crude product by silica gel column chromatography, wherein the eluent is a mixed solution of ethyl acetate/petroleum ether to obtain the 3-aryl-2-propyn-1-ol derivative.
4. The method for preparing 3-aryl-2-propyn-1-ol derivatives according to claim 3, wherein the structural formula of the aryl acetylene compounds in the step one is as follows:
wherein Ar is pyridine, thiophene, naphthalene or
5. A3-aryl-2-propyn-1-ol derivative according to claim 4, wherein the derivative is
Wherein R is alkoxy, alkyl, halogen or phenyl.
6. The process for preparing a 3-aryl-2-propyn-1-ol derivative as claimed in claim 3, wherein the electrolysis in the first step is carried out at a constant current of 10 mA-20 mA; the molar ratio of the aryl acetylene compounds, the ammonium salt, the water and the alkali in the step one is 1:1.8:7: 2; the molar ratio of the aryl acetylene compounds to the organic solvent in the step one is 1mmol:20 mL.
7. The process according to claim 3, wherein the two platinum plate electrodes in the first step each have a size of 10X 0.1mm, and the distance between the two platinum plate electrodes is 2 cm; the alkali in the step one is sodium carbonate, sodium hydroxide or sodium ethoxide; the organic solvent in the first step is anhydrous N, N-dimethylformamide or anhydrous N, N-dimethylacetamide.
8. The process for preparing 3-aryl-2-propyn-1-ol derivatives as claimed in claim 3, wherein the ammonium salt in step one is N, N, N-trimethylanilinium triflate or N, N, N-trimethylbenzylammonium triflate; the structural formula of the N, N, N-trimethylbenzene ammonium trifluoromethanesulfonate is shown in the specification
The structural formula of the N, N, N-trimethylbenzylammonium triflate is shown in the specification
The preparation method of the N, N, N-trimethylbenzene ammonium trifluoromethyl sulfonate comprises the following steps: first, 10mmol of N, N-dimethylaniline and 10mL of CH were added sequentially to a dry round-bottomed flask equipped with a magnetic stirrer2Cl2Then, dropwise adding 11mmol of trifluoromethyl methyl sulfonate at room temperature to obtain a mixed solution; stirring the mixed solution for 4 hours at room temperature to obtain a reaction product, and concentrating by using a rotary evaporator to remove CH in the reaction product2Cl2Obtaining a solid substance; washing with methyl tert-butyl ether for 3 times, and vacuum drying to obtain N, N, N-trimethylbenzene ammonium triflate; the preparation method of the N, N, N-trimethylbenzylammonium triflate is as follows: first, 10mmol of N, N-dimethylbenzylamine and 10mL of CH were sequentially added to a dry round-bottomed flask equipped with a magnetic stirrer2Cl2Obtaining a mixed solution; placing the mixed solution at 0 deg.CDropwise adding 11mmol of methyl trifluoromethanesulfonate into the mixed solution at 0 ℃, and stirring at room temperature for 2 hours to obtain a reaction product; removing CH in the reaction product by concentration of a rotary evaporator2Cl2Obtaining a solid substance; washing 3 times with methyl tert-butyl ether, and finally vacuum drying to obtain the N, N, N-trimethylbenzylammonium triflate.
9. The process for producing a 3-aryl-2-propyn-1-ol derivative according to claim 3, wherein the brine in the second step is a saturated brine; the power supply in the second step is a potentiostat; and the temperature of the reduced pressure distillation in the step two is 35 ℃, and the pressure is 0.1 MPa.
10. The process for preparing 3-aryl-2-propyn-1-ol derivatives as claimed in claim 3, wherein the volume ratio of the reaction mixture to brine in step two is 4: 15; the volume ratio of the ethyl acetate to the petroleum ether in the ethyl acetate/petroleum ether mixed solution in the third step is 1 (2-5).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011030136.9A CN112110800B (en) | 2020-09-25 | 2020-09-25 | 3-aryl-2-propyne-1-alcohol derivative and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011030136.9A CN112110800B (en) | 2020-09-25 | 2020-09-25 | 3-aryl-2-propyne-1-alcohol derivative and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112110800A true CN112110800A (en) | 2020-12-22 |
| CN112110800B CN112110800B (en) | 2022-06-24 |
Family
ID=73797102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011030136.9A Active CN112110800B (en) | 2020-09-25 | 2020-09-25 | 3-aryl-2-propyne-1-alcohol derivative and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112110800B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1266426A (en) * | 1997-08-06 | 2000-09-13 | 诺瓦提斯公司 | Microbicidal N-sulfonylglycin alkynyloxyphenemethyl amide derivatives |
-
2020
- 2020-09-25 CN CN202011030136.9A patent/CN112110800B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1266426A (en) * | 1997-08-06 | 2000-09-13 | 诺瓦提斯公司 | Microbicidal N-sulfonylglycin alkynyloxyphenemethyl amide derivatives |
Non-Patent Citations (3)
| Title |
|---|
| TECLE, HAILE等: "Design and Synthesis of m1-Selective Muscarinic Agonists: (R)-(-)-(Z)-1-Azabicyclo- [2.2.1]heptan-3-one,O-(3-(3"-Methoxyphenyl)-2-propynyl)-oximeMaleate(CI-1017),aFunctionally m1-Selective Muscarinic Agonist", 《JOURNAL OF MEDICINAL CHEMISTRY》, vol. 41, no. 14, 4 June 1998 (1998-06-04), pages 2524 - 2536 * |
| YAO,XIAOQUAN等: "Phosphine-Triggered Complete Chemo-Switch: From Efficient Aldehyde-Alkyne-Amine Coupling to Efficient Aldehyde-Alkyne Coupling in Water", 《ORGANIC LETTERS》, vol. 7, no. 20, 30 August 2005 (2005-08-30), pages 4395 - 4398 * |
| 刘淘陶: "芳基末端炔烃的电化学羟甲基化及硒醚化反应研究", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》, no. 03, 15 March 2022 (2022-03-15), pages 014 - 109 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112110800B (en) | 2022-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113121462B (en) | Preparation method of 5-trifluoromethyl substituted 1,2,3-triazole compound | |
| Jia et al. | Cu (BTC)-MOF catalyzed multicomponent reaction to construct 1, 4-disubstituted-1, 2, 3-triazoles | |
| CN111205279B (en) | Polysubstituted benzodihydrofuran heterocyclic compound and preparation method and application thereof | |
| CN111690947B (en) | Electrochemical synthesis method of trifluoromethylated aryl amide derivative | |
| CN113943252A (en) | Pyrazolidinesulfonyl fluoride compounds and preparation method thereof | |
| CN113735751A (en) | Method for preparing aryl isothiourea | |
| CN112110800B (en) | 3-aryl-2-propyne-1-alcohol derivative and preparation method thereof | |
| CN110272403B (en) | Method for synthesizing carbamate containing dihydrobenzofuran ring and trifluoromethyl | |
| CN113735777B (en) | Method for preparing cyclic thiourea compound | |
| CN112299981B (en) | Preparation method of alpha, alpha-difluoroketone derivative | |
| CN103694182B (en) | A kind of preparation method of quinoxaline compound | |
| CN113735752B (en) | Method for preparing isothiourea compound based on substituted iodobenzene | |
| CN108864173B (en) | Process for converting substituted sodium arylsulfinates into aryltri-n-butyltin | |
| CN112142732B (en) | Preparation method of chiral indolizidine compound | |
| CN109678862B (en) | Preparation method of polysubstituted distyryl indole derivative | |
| CN109734667B (en) | Polysubstituted imidazole compound and synthesis method and application thereof | |
| CN111217847A (en) | Thiosilane ligand, preparation method thereof and application thereof in aryl boronization catalytic reaction | |
| CN108484451A (en) | A kind of method that one kettle way prepares 1,2- alkamine compounds | |
| CN112979693B (en) | Alkyl trimethyl tin compounds, and preparation method and application thereof | |
| CN110256349B (en) | Polysubstituted pyrazoles and process for their preparation | |
| CN106883153A (en) | A kind of preparation method of the amphyl of 2 sulfonyl 1,4 2 | |
| CN111732508B (en) | Synthesis method of spiro compound | |
| CN113200980A (en) | Method for synthesizing indolizine compound under catalysis of silver | |
| Wang et al. | Preparation of ferrocenyl imidazolines using bis (triphenyl) oxodiphosphonium trifluoromethanesulfonate | |
| CN118125897A (en) | Synthetic method for preparing monofluoroolefin from organoboron compound |
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 |