CN110878080A - Preparation method of 3-thiophenecarboxaldehyde - Google Patents
Preparation method of 3-thiophenecarboxaldehyde Download PDFInfo
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- CN110878080A CN110878080A CN201911252079.6A CN201911252079A CN110878080A CN 110878080 A CN110878080 A CN 110878080A CN 201911252079 A CN201911252079 A CN 201911252079A CN 110878080 A CN110878080 A CN 110878080A
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- 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
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Abstract
The invention discloses a preparation method of 3-thiophenecarboxaldehyde, which comprises the following steps: mixing 3-methylthiophene and an organic solvent, heating to a first temperature, keeping the first temperature unchanged, respectively adding azodiisobutyronitrile and N-halogenated succinimide, keeping the temperature at the first temperature for a period of time, cooling, and filtering to obtain a mixed solution of the 3-halogenated methylthiophene; adding N-methylmorpholine-N-oxide into the mixed solution of the 3-halogenated methyl thiophene without any treatment, heating to a second temperature, cooling, washing with water, desolventizing to obtain a crude product, and further rectifying to obtain the pure 3-thiophenecarboxaldehyde. The invention overcomes the problems of poor selectivity, low yield and the like in the existing synthesis method, and is a method which has high selectivity and high yield and can synthesize the 3-thiophenecarboxaldehyde under mild reaction conditions; the preparation method disclosed by the invention is simple to operate, free of irritation, easy to obtain raw materials, and suitable for industrial production of 3-thiophenecarboxaldehyde, and the operation cost and the raw material cost are saved.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of 3-thiophenecarboxaldehyde.
Background
The 3-thiophenecarboxaldehyde is a colorless or light yellow liquid, the color of the solution gradually becomes dark after being exposed to light, the solution has pungent smell, and the solution is easily dissolved in organic solvents such as alcohol, benzene, ether, dichloromethane and the like and is slightly soluble in water. 3-thiophenecarboxaldehyde is an important medical intermediate, is mainly used for amine antibacterial and anti-inflammatory drugs, and is used for treating infection of staphylococcus, streptococcus, pneumococcus and meningococcus. A large amount of 3-thiophenecarboxaldehyde is needed as a starting raw material for a new anti-HIV drug newly developed in the pfeiffe pharmacy at present, but the 3-thiophenecarboxaldehyde is not developed sufficiently in China, the production capacity is low, the market supply of the drug is restricted, and a new production method suitable for industrialization is urgently needed in the market.
A method for synthesizing 3-thiophenecarboxaldehyde is also disclosed in the prior art, and for example, the literature (ABENZODITHIOPHENE-BASED SEMICONDUCTING POLYMER FOR ORGANIC THIN FILM TRANSISTOR, Bulletin of the Korea Chemical Society, 2013, 34(4), 1170-1174) reports a method for synthesizing 3-thiophenecarboxaldehyde, in which 3-bromothiophene is used as a raw material and reacted with n-butyllithium at-78 ℃ to obtain 3-thiophenecarboxaldehyde, the temperature required in the route is extremely low, the route is not suitable for industrialization, and n-butyllithium is extremely liable to generate heat and burn when contacting with water, oxides and the like, and is liable to catch fire, and is very dangerous to use. The reaction equation is as follows:
as another example, the literature (Synthetic Communications, 2001, 31(10), 1527-: 1, 4-dithio-2, 5-diol is used as a raw material to synthesize 2, 5-dihydro-3-thiophenecarboxaldehyde, and then the 2, 5-dihydro-3-thiophenecarboxaldehyde and sulfuryl chloride are synthesized into 3-thiophenecarboxaldehyde at the temperature of minus 35 ℃. The first step of the route needs steam distillation and is not easy to amplify, the second step needs reaction at an extremely low temperature, once the temperature is slightly high, impurities are easy to generate, the requirement on equipment is harsh, special low-temperature equipment is needed, the energy consumption is high, and the amplification is not easy. The reaction equation is as follows:
therefore, it is clear that the above-mentioned existing methods for preparing 3-thiophenecarboxaldehyde still have inconveniences and disadvantages in the aspects of method and use, and further improvement is needed. In order to solve the problems of the preparation method of 3-thiophenecarboxaldehyde, related manufacturers have no time to think about the solution, but no suitable design has been developed and completed for a long time, and the general method has no appropriate method to solve the problems, which is obviously a problem to be solved by related manufacturers.
In view of the above-mentioned drawbacks of the existing 3-thiophenecarboxaldehyde preparation method, the present inventors have conducted active research and innovation based on practical experience and professional knowledge that is rich over many years in the design and manufacture of such products, and with the application of theory, in order to create a new 3-thiophenecarboxaldehyde preparation method, which can improve the existing 3-thiophenecarboxaldehyde preparation method and make it more practical. After continuous research and design and repeated trial and improvement, the invention with practical value is finally created.
Disclosure of Invention
The invention mainly aims to overcome the defects of the existing preparation method of 3-thiophenecarboxaldehyde, and provides a novel preparation method of 3-thiophenecarboxaldehyde, which can effectively solve the problems of high requirements on equipment and temperature, high energy consumption, high cost and difficulty in industrial production in the existing preparation method. The preparation method disclosed has the advantages of mild conditions, easily obtained raw materials, stable supply and low cost; and the prepared 3-thiophenecarboxaldehyde has the advantages of high purity and high yield, thereby being more suitable for practical use and having industrial utilization value.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme.
The invention provides a preparation method of 3-thiophenecarboxaldehyde, which comprises the following steps:
(1) mixing 3-methylthiophene with an organic solvent, heating to a first temperature, keeping the first temperature unchanged, respectively adding azodiisobutyronitrile and N-halogenated succinimide, carrying out heat preservation reaction at the first temperature for a period of time, then cooling, and then filtering to obtain a mixed solution of the 3-halogenated methylthiophene;
(2) adding N-methylmorpholine-N-oxide into the obtained mixed solution of the 3-halogenated methyl thiophene without any treatment, heating to a second temperature for reaction, cooling, washing with water, desolventizing to obtain a crude product, and further rectifying to obtain the pure 3-thiophenecarboxaldehyde.
The preparation method described above, wherein the organic solvent in step (1) is selected from one or more of ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate, dichloromethane, chloroform, and carbon tetrachloride.
In the preparation method, in the step (1), the 3-methylthiophene and the organic solvent are mixed in an amount of 1 (2-10) by mass ratio.
The preparation method described above, wherein the N-halogenated succinimide in the step (1) is one or more selected from N-chlorosuccinimide, N-bromosuccinimide, and N-iodosuccinimide.
In the preparation method, in the step (1), the first temperature is 40 to 100 ℃, and the reaction time is 0.5 to 5 hours.
In the preparation method, in the step (1), the first temperature is 70-80 ℃, and the reaction time is 1-3 hours.
In the preparation method, in the step (1), the molar ratio of the N-halogenated succinimide to the 3-methylthiophene is (0.7-1.1): 1.
In the preparation method, in the step (1), the molar ratio of the azobisisobutyronitrile to the 3-methylthiophene is (0.10-0.30): 1.
The preparation method described above, wherein the N-methylmorpholine-N-oxide in the step (2) is a solid or a 5% to 90% aqueous solution.
In the preparation method, in the step (2), the second temperature is 20 to 80 ℃, and the reaction time is 4 to 8 hours.
In the preparation method, in the step (2), the second temperature is 40-60 ℃, and the reaction time is 5-7 hours.
In the preparation method, the mixed solution of the N-methylmorpholine-N-oxide and the 3-halogenated methylthiophene in the step (2) is mixed in a molar ratio of (1.0-6.0): 1.
By the technical scheme, the invention (name) at least has the following advantages:
(1) the invention can prepare the 3-thiophenecarboxaldehyde with the purity of over 99.0 percent through rectification, and the yield of the 3-thiophenecarboxaldehyde is higher.
(2) The intermediate produced in the first step of reaction of the invention does not need to be treated, and the second step of reaction can be directly carried out, thereby avoiding the pollution of irritant products to workplaces and protecting the health of workers. The preparation method disclosed by the invention does not need to react under an ultralow temperature condition, is simple to operate, does not need low-temperature equipment, saves the operation cost and energy consumption, and is simple in steps, mild in conditions and relatively environment-friendly.
(3) More importantly, the raw material 3-methylthiophene used in the invention is cheap, easy to obtain and stable in supply.
(4) The method overcomes the problems of poor selectivity, low yield and the like in the conventional synthesis method, is a method for synthesizing the 3-thiophenecarboxaldehyde under mild reaction conditions with high selectivity and high yield, is simple to operate, has easily obtained raw materials, saves the operation cost and the raw material cost, and is suitable for industrial production of the 3-thiophenecarboxaldehyde.
In conclusion, the special preparation method of the 3-thiophenecarboxaldehyde effectively solves the problems of poor selectivity, low yield and the like in the existing synthesis method. The method has the advantages and practical value, does not have similar design publication or use but is really innovative in the similar methods, has great improvement on the method or the function, has great progress in the technology, produces good and practical effects, has multiple enhanced effects compared with the existing preparation method of the 3-thiophenecarboxaldehyde, is more practical, has industrial wide utilization value, and is a novel, improved and practical new design.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
The specific process steps of the present invention are detailed in the following examples.
Detailed Description
The present invention is further illustrated below with reference to examples, which are intended to illustrate the invention and not to limit the scope of the invention. Furthermore, it should be understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the teachings herein, and such equivalents may fall within the scope of the invention as defined in the appended claims.
It is to be noted that the experimental methods used in the following examples are all conventional methods unless otherwise specified. The materials and reagents used in the examples are commercially available unless otherwise specified.
The preparation process as described herein is carried out according to the following reaction equation:
wherein the content of the first and second substances,
1: mixing 3-methylthiophene and an organic solvent, heating to a first temperature, keeping the first temperature unchanged, respectively adding azodiisobutyronitrile and N-halogenated succinimide, keeping the temperature at the first temperature for a period of time, cooling, and filtering to obtain a mixed solution of the 3-halogenated methylthiophene;
2: and adding N-methylmorpholine-N-oxide into the obtained mixed solution of the 3-halogenated methyl thiophene, heating to a second temperature, cooling, washing with water, desolventizing to obtain a crude product, and further rectifying to obtain the pure 3-thiophenecarboxaldehyde.
The details are described in the examples below.
Example 1
Adding 35.2g of 3-methylthiophene and 206g of ethyl acetate into a three-neck flask, heating the system to 70 ℃, then adding 11.71g of azodiisobutyronitrile and 45.23g N-chlorosuccinimide (NCS) in batches at the temperature, keeping the temperature at 70 ℃ after the addition is finished, reacting for 2 hours, cooling, and filtering to remove precipitated solids to obtain an ethyl acetate solution of 3-chloromethylthiophene.
Adding 125.3g of NMO solid (N-methylmorpholine-N-oxide) into the ethyl acetate solution of the 3-chloromethyl thiophene, heating the system to 50 ℃ for reaction for 6h, cooling, washing with water, desolventizing after the central control reaction is completed, obtaining 23.6g of 3-thiophenecarboxaldehyde, obtaining 58.69% of yield, and further rectifying to obtain a pure product of the 3-thiophenecarboxaldehyde.
Example 2
Adding 37.6g of 3-methylthiophene and 231g of ethyl acetate into a three-neck flask, heating the system to 70 ℃, then adding 12.58g of azodiisobutyronitrile and 64.76g N-bromosuccinimide (NBS) in batches at the temperature, keeping the temperature at 70 ℃ after the addition is finished, reacting for 2 hours, cooling, and filtering to remove precipitated solids to obtain an ethyl acetate solution of the 3-bromomethylthiophene.
134.61g of NMO solid (N-methylmorpholine-N-oxide) is added into the ethyl acetate solution of the 3-bromomethylthiophene, the system is heated to 50 ℃ for reaction for 6h, after the middle control reaction is completed, the temperature is reduced, water washing and desolventizing are carried out, 26.7g of 3-thiophenecarboxaldehyde is obtained, the yield is 62.16%, and the pure 3-thiophenecarboxaldehyde is obtained by further rectification.
Example 3
Adding 34.9g of 3-methylthiophene and 202g of ethyl acetate into a three-neck flask, heating the system to 70 ℃, then adding 11.68g of azodiisobutyronitrile and 60.11g N-bromosuccinimide (NBS) in batches at the temperature, keeping the temperature at 70 ℃ after the addition is finished, reacting for 2 hours, cooling, and filtering to remove precipitated solids to obtain an ethyl acetate solution of the 3-bromomethylthiophene.
249.89g of NMO aqueous solution (N-methylmorpholine-N-oxide) with the mass fraction of 50% is dropwise added into the ethyl acetate solution of the 3-bromomethylthiophene, the system is heated to 50 ℃ to react for 6 hours, after the central control reaction is completed, the temperature is reduced, water washing and desolventizing are carried out to obtain 18.6g of 3-thiophenecarboxaldehyde, the yield is 46.65%, and the 3-thiophenecarboxaldehyde pure product is obtained by further rectification.
Example 4
Adding 39.8g of 3-methylthiophene and 283g of carbon tetrachloride into a three-neck flask, heating the system to slightly reflux, then adding 13.32g of azodiisobutyronitrile and 68.55g N-bromosuccinimide (NBS) in batches at the temperature, keeping the temperature at 70 ℃ after the addition is finished, reacting for 2 hours, cooling, and filtering to remove precipitated solids to obtain the carbon tetrachloride solution of the 3-bromomethylthiophene.
142.49g of NMO solid (N-methylmorpholine-N-oxide) is added into the ethyl acetate solution of the 3-bromomethylthiophene, the system is heated to 50 ℃ for reaction for 6h, after the middle control reaction is completed, the temperature is reduced, water washing and desolventizing are carried out, 30.4g of 3-thiophenecarboxaldehyde is obtained, the yield is 66.86%, and the 3-thiophenecarboxaldehyde pure product is obtained by further rectification.
Example 5
Adding 33.7g of 3-methylthiophene and 240g of carbon tetrachloride into a three-neck flask, heating the system to slightly reflux, then adding 11.27g of azodiisobutyronitrile and 58.05g N-bromosuccinimide (NBS) in batches at the temperature, keeping the temperature at 70 ℃ after the addition is finished, reacting for 2 hours, cooling, and filtering to remove precipitated solids to obtain the carbon tetrachloride solution of the 3-bromomethylthiophene.
120.65g of NMO solid (N-methylmorpholine-N-oxide) is added into the ethyl acetate solution of the 3-bromomethylthiophene, the system is heated to 70 ℃ for reaction for 6h, after the middle control reaction is completed, the temperature is reduced, water washing and desolventizing are carried out, 22.19g of 3-thiophenecarboxaldehyde is obtained, the yield is 57.6%, and the pure 3-thiophenecarboxaldehyde is obtained by further rectification.
Example 6
Adding 35.2g of 3-methylthiophene and 71g of isopropyl acetate into a three-neck flask, heating the system to 80 ℃, then adding 11.71g of azodiisobutyronitrile and 45.23g N-chlorosuccinimide (NCS) in batches at the temperature, keeping the temperature at 80 ℃ after the addition is finished, reacting for 1h, cooling, and filtering to remove precipitated solids to obtain an isopropyl acetate solution of 3-chloromethylthiophene.
Adding 125.3g of NMO solid (N-methylmorpholine-N-oxide) into the isopropyl acetate solution of the 3-chloromethyl thiophene, heating the system to 60 ℃ for reaction for 4 hours, cooling, washing with water, desolventizing after the middle control reaction is completed, obtaining 18.71g of 3-thiophenecarboxaldehyde, obtaining the yield of 57.6 percent, and further rectifying to obtain the pure 3-thiophenecarboxaldehyde.
In conclusion, the invention can prepare the 3-thiophenecarboxaldehyde with the purity of more than 99.0 percent through rectification, and the yield of the 3-thiophenecarboxaldehyde is higher. The intermediate produced in the first step of reaction of the invention does not need to be treated, and the second step of reaction can be directly carried out, thereby avoiding the pollution of irritant products to workplaces and protecting the health of workers. The preparation method disclosed by the invention does not need to react under an ultralow temperature condition, is simple to operate, does not need low-temperature equipment, saves the operation cost and energy consumption, and is simple in steps, mild in conditions and relatively environment-friendly. More importantly, the raw material 3-methylthiophene used in the invention is cheap, easy to obtain and stable in supply. The method overcomes the problems of poor selectivity, low yield and the like in the conventional synthesis method, is a method for synthesizing the 3-thiophenecarboxaldehyde under mild reaction conditions with high selectivity and high yield, is simple to operate, has easily obtained raw materials, saves the operation cost and the raw material cost, and is suitable for industrial production of the 3-thiophenecarboxaldehyde.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (12)
1. A preparation method of 3-thiophenecarboxaldehyde, wherein the method comprises the following steps:
(1) mixing 3-methylthiophene with an organic solvent, heating to a first temperature, keeping the first temperature unchanged, respectively adding azodiisobutyronitrile and N-halogenated succinimide, carrying out heat preservation reaction at the first temperature for a period of time, then cooling, and then filtering to obtain a mixed solution of the 3-halogenated methylthiophene;
(2) adding N-methylmorpholine-N-oxide into the obtained mixed solution of the 3-halogenated methyl thiophene without any treatment, heating to a second temperature for reaction, cooling, washing with water, desolventizing to obtain a crude product, and further rectifying to obtain the pure 3-thiophenecarboxaldehyde.
2. The preparation method according to claim 1, wherein the organic solvent in step (1) is selected from one or more of ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate, dichloromethane, chloroform, and carbon tetrachloride.
3. The production method according to claim 1, wherein the 3-methylthiophene and the organic solvent are mixed in the step (1) in an amount of 1 (2 to 10) by mass.
4. The method according to claim 1, wherein the N-halogenated succinimide in the step (1) is selected from one or more of N-chlorosuccinimide, N-bromosuccinimide, and N-iodosuccinimide.
5. The preparation method according to claim 1, wherein the first temperature in the step (1) is 40 to 100 ℃, and the incubation reaction time is 0.5 to 5 hours.
6. The preparation method according to claim 1, wherein the first temperature in the step (1) is 70 to 80 ℃, and the incubation reaction time is 1 to 3 hours.
7. The preparation method according to claim 1, wherein the molar ratio of the N-halogenated succinimide to the 3-methylthiophene in the step (1) is (0.7-1.1): 1.
8. The production process according to claim 1, wherein the molar ratio of azobisisobutyronitrile to 3-methylthiophene in the step (1) is (0.10 to 0.30): 1.
9. The method according to claim 1, wherein the N-methylmorpholine-N-oxide in step (2) is a solid or a 5-90% aqueous solution.
10. The preparation method according to claim 1, wherein the second temperature in the step (2) is 20 to 80 ℃, and the reaction time is 4 to 8 hours.
11. The method according to claim 1, wherein the second temperature in the step (2) is 40 to 60 ℃, and the reaction time is 5 to 7 hours.
12. The method according to claim 1, wherein the mixed solution of N-methylmorpholine-N-oxide and 3-halomethylthiophene in the step (2) is mixed in an amount of (1.0-6.0): 1 in a molar ratio.
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| CN106588868A (en) * | 2016-11-16 | 2017-04-26 | 武汉理工大学 | Synthesis method of 2-bromo-3-thiophenic acid intermediate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106588868A (en) * | 2016-11-16 | 2017-04-26 | 武汉理工大学 | Synthesis method of 2-bromo-3-thiophenic acid intermediate |
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| MASAYUKI TABATA: "One-Pot Transformation of Methylarenes into Aromatic Aldehydes underMetal-Free Conditions", 《EUR. J. ORG. CHEM.》 * |
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Application publication date: 20200313 |