CN109321940A - A kind of the electrochemical oxidation synthetic method and its application of amide - Google Patents
A kind of the electrochemical oxidation synthetic method and its application of amide Download PDFInfo
- Publication number
- CN109321940A CN109321940A CN201811457424.5A CN201811457424A CN109321940A CN 109321940 A CN109321940 A CN 109321940A CN 201811457424 A CN201811457424 A CN 201811457424A CN 109321940 A CN109321940 A CN 109321940A
- Authority
- CN
- China
- Prior art keywords
- amide
- synthetic method
- electrochemical oxidation
- reaction
- reactant
- 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.)
- Pending
Links
Classifications
-
- 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
- C25B3/20—Processes
- C25B3/23—Oxidation
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
The invention discloses a kind of electrochemical oxidation synthetic method of amide and its applications, belong to electrochemistry technical field of organic synthesis.Using thiocarboxylic acid or dithionate and amine as reaction raw materials in amide synthetic method disclosed by the invention, it aoxidizes thiocarboxylic acid or dithionate to form free radical intermediate by the anode in electrolytic cell first, latter two right free radical intermediate carries out coupling and forms crucial intermediate disulfide, and disulfide occurs nucleophilic addition-elimination reaction with reactant amine again and generates amide compound.Synthetic method of the invention does not need to add any catalyst, and reaction condition is mild, and by-product is few, is conducive to the synthesis and purifying of amide compound, and amides drug is prepared in pharmaceutical synthesis and is widely used.
Description
Technical field
The invention belongs to electrochemistry technical field of organic synthesis, and in particular to a kind of electrochemical oxidation synthetic method of amide
And its application.
Background technique
Amido bond is not only the composition of the main skeleton structure of many natural products (such as: polypeptide, protein and chitin)
Part, and be also very in many organic compounds (such as: catalyst, drug, agricultural chemicals and organic functional material)
One of important functional group.There are amido bonds in 2/3rds drug candidate for investigation discovery in 2006;Prescription in 2016
Before drug product amount in 200 drug, contain amido bond in the medicines structure that has 24%.Drug of the amido bond in many high sales volumes
In be crucial structure, such as: fentanyl, Aripiprazole, Imatinib, lidocaine, Ambien and lenalidomide, structural formula is such as
Shown in Fig. 2.
In last decade, as acyl group source, synthesizing amide has attracted and has more and more had thiocarboxylic acid in a mild condition
The interest of chemical machine man.Up to the present, two kinds of main modes have been had developed to activate thiocarboxylic acid with synthesizing amide
Close object, as shown in Figure 3: the first be by thiocarboxylic acid first with some activating reagents for example Sanger reagent, Mukaiyama reagent,
Organic isocyanide, copper reagent and nitroso organic matter form active sulfur-bearing intermediate, these intermediates can be anti-with amine
Amide (Fig. 3 a) should be generated;Another method is that thiocarboxylic acid is first converted into disulphide, and this disulphide can be close
Then core addition is eliminated and generates amide, have several seminars to report the method for converting disulphide for thiocarboxylic acid: Gopi
Seminar uses copper sulphate to generate disulphide as coupling reagent catalysis thiocarboxylic acid;Tan seminar Tris(2,2'- bipyridyl) ruthenium (II) chloride
Photochemical catalytic oxidation thiocarboxylic acid potassium generates disulphide;Biswas seminar uses cadmium sulfide nano-particles as Heterogeneous photocatalysis
Thiocarboxylic acid is oxidized to disulphide (Fig. 3 b) by agent.Although these reported strategies are quite effective, these strategies are still
So there is some shortcomings, such as: many activating reagents are toxic and need the amount of stoichiometry, some need metal, some need
Expensive catalyst.
Therefore, it is highly desirable the more sustainable and green method with thiocarboxylic acid synthesizing amide of development, to avoid
The use of catalyst and toxic reagent.
Summary of the invention
In view of this, one of the objects of the present invention is to provide a kind of electrochemical oxidation synthetic methods of amide;The present invention
The second purpose be that the electrochemical oxidation synthetic method for providing a kind of amide prepares answering for amides drug in pharmaceutical synthesis
With.
For achieving the above object, the invention provides the following technical scheme:
1, a kind of electrochemical oxidation synthetic method of amide, the reaction formula of the synthetic method are as follows:
The reactant I is thiocarboxylic acid or dithionate, and the reactant II is primary amine, secondary amine, wherein R1For
Chain-like alkyl, naphthenic base or phenyl and its derivative, R2For H, alkyl or phenyl and its derivative, R3For H, alkyl or
Phenyl and its derivative.
Further, the synthetic method the following steps are included:
1) electrochemical oxidation: reactant I and reactant II being added in reactor first, and electrolyte, organic solvent is added
And stirrer, two platinum plate electrodes are secondly installed in the reactor respectively as cathode and anode, and galvanization carries out electrochemistry
Oxidation reaction;
2) it washs drying: the mixture in step 1) after reaction in reactor being filtered, filtrate is taken successively to use
It is saturated NaHCO3Solution, saturated salt solution and pure water carry out washing extraction, will wash organic phase extracted and be done with desiccant
Rotary evaporation concentration is carried out after dry, obtains crude product;
3) amide compound purifies: crude product being purified by column chromatography, obtains amide III.
Further, the organic solvent includes appointing in acetonitrile, methylene chloride, acetone, tetrahydrofuran or ethyl acetate
It anticipates one kind.
Further, the electrolyte includes tetrabutyl ammonium tetrafluoroborate, tetrabutyl ammonium hexafluorophosphate, the tetrabutyl to toluene sulphur
Any one in sour ammonium, tetrabutyl ammonium acetate, lithium perchlorate or sodium tetrafluoroborate.
Further, the specification of the platinized platinum is 1.0cm × 1.0cm, and the electric current is 1.0~12.0mA.
Further, the concentration of the electrolyte is 0.1mol/L.
Further, the reaction time of the electrochemical oxidation reactions be 12~for 24 hours.
Further, the desiccant is anhydrous sodium sulfate.
Further, the eluant, eluent of the column chromatography is that the petroleum ether that volume ratio is 2~10:1 is mixed with what ethyl acetate formed
Bonding solvent.
2, a kind of electrochemical oxidation synthetic method of amide prepares the application of amides drug in pharmaceutical synthesis.
The beneficial effects of the present invention are: a kind of electrochemical oxidation synthetic method of amide provided by the invention, it is logical first
The anode crossed in electrolytic cell aoxidizes thiocarboxylic acid or dithionate to form free radical intermediate, in latter two right free radical
Mesosome carries out coupling and forms crucial intermediate disulfide, and disulfide occurs nucleophilic with another reactant amine again and adds
At-elimination reaction generation amide compound.Synthetic method of the invention does not need any catalyst, and reaction condition is mild,
By-product is few, is conducive to the synthesis and purifying of amide compound, obtains the amide compound of high yield, make in pharmaceutical synthesis
Standby amides drug has a wide range of applications.
Detailed description of the invention
In order to keep the purpose of the present invention, technical scheme and beneficial effects clearer, the present invention provides following attached drawing:
Fig. 1 is a kind of reaction formula figure of the electrochemical oxidation synthetic method of amide of the present invention;
Fig. 2 is the high sales volume medicines structure figure with amido bond;
Fig. 3 is conventional amide chemical combination object reaction principle figure;
Fig. 4 is that the cyclic voltammetry of reactant in the embodiment of the present invention 1 detects figure;
Fig. 5 is a kind of reaction mechanism figure of the electrochemical oxidation synthetic method of amide of the present invention.
Specific embodiment
Below by a preferred embodiment of the present invention will be described in detail.The experiment of actual conditions is not specified in embodiment
Method, usually according to conventional conditions or according to the manufacturer's recommendations.
Embodiment 1
Influence of the different dielectrics to electrochemical oxidation synthesizing amide:
Reaction formula is as shown in Figure 1:
(1) electrochemical oxidation: the thioacetic acid potassium of 1mmol and 0.5mmol aniline being added in reaction tube first, are added
The tetrabutyl ammonium tetrafluoroborate of 0.50mmol makees electrolyte, the acetonitrile of 5.0mL is solvent and stirrer, installs in reaction tube
The platinum plate electrode of two 1.0cm × 1.0cm is reacted for 24 hours after leading to the electric current of 1.0mA respectively as cathode and anode;
(2) it washs drying: mixture after reaction is filtered, take filtrate successively with saturation NaHCO3Solution,
Saturated salt solution and pure water carry out washing extraction, will wash after organic phase extracted is dried with anhydrous sodium sulfate and rotate
Evaporation, obtains crude product;
(3) amide compound purifies: crude product being purified by column chromatography, eluant, eluent is the stone that volume ratio is 2:1
Oily ether and ethyl acetate mixed solvent, obtain amide product III1, yield 63%, structural formula is as follows:
With same technical solution, there are not amide product III1, i.e. amide compound when electrolyte being not added in reaction system
Yield be 0%;And tetrabutyl ammonium hexafluorophosphate, tetrabutyl paratoluenesulfonic acid ammonium salt, tetrabutyl ammonium acetate, lithium perchlorate are used respectively
Or sodium tetrafluoroborate as electrolyte when its amide product III1 yield be respectively 57%, 29%, 84%, 20%, 57%.
Embodiment 2
Influence of the different organic solvents to electrochemical oxidation synthesizing amide:
(1) electrochemical oxidation: the thioacetic acid potassium of 1mmol and 0.5mmol aniline being added in reaction tube first, are added
The tetrabutyl ammonium tetrafluoroborate of 0.50mmol makees electrolyte, the methylene chloride of 5.0mL is solvent and stirrer, in reaction tube
The platinum plate electrode of two 1.0cm × 1.0cm is installed respectively as cathode and anode, is reacted for 24 hours after leading to the electric current of 1.0mA;
(2) it washs drying: mixture after reaction is filtered, take filtrate successively with saturation NaHCO3Solution,
Saturated salt solution and pure water carry out washing extraction, will wash after organic phase extracted is dried with anhydrous sodium sulfate and rotate
Evaporation, obtains crude product;
(3) amide compound purifies: crude product being purified by column chromatography, eluant, eluent is the stone that volume ratio is 2:1
Oily ether and ethyl acetate mixed solvent, obtain amide product III1, yield 46%.
With same technical solution, its amide when using acetone, tetrahydrofuran or ethyl acetate respectively as organic solvent
The yield of product III1 is respectively 48%, 63%, 97%.
Embodiment 3
(1) electrochemical oxidation: the thioacetic acid potassium of 1mmol and 0.5mmol aniline being added in reaction tube first, are added
The tetrabutyl ammonium tetrafluoroborate of 0.50mmol makees electrolyte, the ethyl acetate of 5.0mL is solvent and stirrer, in reaction tube
The platinum plate electrode of two 1.0cm × 1.0cm is installed respectively as cathode and anode, carries out reaction 12h after leading to the electric current of 12.0mA;
(2) it washs drying: mixture after reaction is filtered, take filtrate successively with saturation NaHCO3Solution,
Saturated salt solution and pure water carry out washing extraction, will wash after organic phase extracted is dried with anhydrous sodium sulfate and rotate
Evaporation, obtains crude product;
(3) amide compound purifies: crude product being purified by column chromatography, eluant, eluent is the stone that volume ratio is 2:1
Oily ether and ethyl acetate mixed solvent, obtain amide product III1, yield 63%.
Embodiment 4
Influence of the three-dimensional effect of reactant II to electrochemical oxidation synthesizing amide:
(1) reaction tube electrochemical oxidation: is added in the thioacetic acid potassium of 1mmol and 0.5mmol o-toluidine first
In, be added 0.50mmol tetrabutyl ammonium tetrafluoroborate make electrolyte, 5.0mL ethyl acetate be solvent and stirrer,
The platinum plate electrode of two 1.0cm × 1.0cm is installed respectively as cathode and anode in reaction tube, the electric current for leading to 1.0mA is laggard
Row reaction is for 24 hours;
(2) it washs drying: mixture after reaction is filtered, take filtrate successively with saturation NaHCO3Solution,
Saturated salt solution and pure water carry out washing extraction, will wash after organic phase extracted is dried with anhydrous sodium sulfate and rotate
Evaporation, obtains crude product;
(3) amide compound purifies: crude product being purified by column chromatography, eluant, eluent is the stone that volume ratio is 2:1
Oily ether and ethyl acetate mixed solvent, obtain amide product III2, yield 78%.
Reactant II is being changed to m-toluidine and open-chain crown ether respectively, other reaction conditions are constant, obtained acyl
The yield of amine product III is respectively III3 (97%), III4 (96%), and structural formula is as follows:
The yield different from III2-III4 can be seen that the yield of electrochemical oxidation reactions synthesizing amide of the invention by
The influence of the three-dimensional effect of object II is answered, the three-dimensional effect of reactant II is bigger, then the yield of caused amide is lower.
Embodiment 5
Influence of the electronic effect of reactant II to electrochemical oxidation synthesizing amide:
(1) thioacetic acid potassium of 1mmol electrochemical oxidation: is reacted into examination with the addition of 0.5mmol P-nethoxyaniline first
Guan Zhong, be added 0.50mmol tetrabutyl ammonium tetrafluoroborate make electrolyte, 5.0mL ethyl acetate be solvent and stirrer,
The platinum plate electrode of two 1.0cm × 1.0cm is installed respectively as cathode and anode in reaction tube, the electric current for leading to 1.0mA is laggard
Row reaction is for 24 hours;
(2) it washs drying: mixture after reaction is filtered, take filtrate successively with saturation NaHCO3Solution,
Saturated salt solution and pure water carry out washing extraction, will wash after organic phase extracted is dried with anhydrous sodium sulfate and rotate
Evaporation, obtains crude product;
(3) amide compound purifies: crude product being purified by column chromatography, eluant, eluent is the stone that volume ratio is 2:1
Oily ether and ethyl acetate mixed solvent, obtain amide product III2, yield 78%.
Reactant II is being changed to para-fluoroaniline, parachloroanilinum, para-bromoaniline and paraiodoaniline, other reaction conditions respectively
Constant, the yield of obtained amide product III is respectively III5 (99%), III6 (88%), III7 (92%), III8
(85%), the structural formula of III9 (86%), III5~III9 is as follows:
The yield different from III5~III9 can be seen that the yield of electrochemical oxidation reactions synthesizing amide of the invention by
The influence of the electronic effect of reactant II.
Embodiment 5
Influence of the electronegativity of reactant II to electrochemical oxidation synthesizing amide:
(1) electrochemical oxidation: (trifluoro) methylaniline is added by the thioacetic acid potassium of 1mmol and 0.5mmol first
In reaction tube, the tetrabutyl ammonium tetrafluoroborate that 0.50mmol is added makees electrolyte, the ethyl acetate of 5.0mL is solvent and stirring
Son installs the platinum plate electrode of two 1.0cm × 1.0cm respectively as cathode and anode in reaction tube, leads to the electric current of 1.0mA
After reacted for 24 hours;
(2) it washs drying: mixture after reaction is filtered, take filtrate successively with saturation NaHCO3Solution,
Saturated salt solution and pure water carry out washing extraction, will wash after organic phase extracted is dried with anhydrous sodium sulfate and rotate
Evaporation, obtains crude product;
(3) amide compound purifies: crude product being purified by column chromatography, eluant, eluent is the stone that volume ratio is 2:1
Oily ether and ethyl acetate mixed solvent, obtain amide product III10, yield 73%.
It is changed to by reactant II to (trimethyl) methylaniline, other reaction conditions are constant, obtained amide product
The yield of III11 is that 96%, III10 and III11 structural formula is as follows:
The yield different from III11 from III10 can be seen that the yield of electrochemical oxidation reactions synthesizing amide of the invention
It is influenced by the electronegativity of reactant II, the electronegativity of reactant II is bigger, then the yield of caused amide is lower.
Embodiment 6
Influence of the substitution degree of N atom to electrochemical oxidation synthesizing amide in reactant II:
(1) thioacetic acid potassium of 1mmol electrochemical oxidation: is reacted into examination with the addition of the methylbenzyl amine of 0.5mmol first
Guan Zhong, be added 0.50mmol tetrabutyl ammonium tetrafluoroborate make electrolyte, 5.0mL ethyl acetate be solvent and stirrer,
The platinum plate electrode of two 1.0cm × 1.0cm is installed in reaction tube respectively as cathode and anode, after leading to the electric current of 1.0mA
It is reacted for 24 hours;
(2) it washs drying: mixture after reaction is filtered, take filtrate successively with saturation NaHCO3Solution,
Saturated salt solution and pure water carry out washing extraction, will wash after organic phase extracted is dried with anhydrous sodium sulfate and rotate
Evaporation, obtains crude product;
(3) amide compound purifies: crude product being purified by column chromatography, eluant, eluent is the stone that volume ratio is 5:1
Oily ether and ethyl acetate mixed solvent, obtain amide product III12, yield 39%.
Reactant II is being changed to benzylamine, other reaction conditions are constant, and the yield of obtained amide product III13 is
80%, III12 and III13 structural formula are as follows:
The yield different from III13 from III12 can be seen that the yield of electrochemical oxidation reactions synthesizing amide of the invention
It is influenced by the substitution degree of N atom in reactant II, the substitution degree of N atom is lower, then participates in reaction as reactant and obtain
Amide compound yield it is higher.
Embodiment 6
Reactant I with different substituents passes through electrochemical oxidation synthesizing amide:
(1) electrochemical oxidation: the aniline of the Thiobutyric acid of 1mmol and 0.5mmol being added in reaction tube first, are added
The tetrabutyl ammonium tetrafluoroborate of 0.50mmol makees electrolyte, the ethyl acetate of 5.0mL is solvent and stirrer, in reaction tube
The platinum plate electrode of two 1.0cm × 1.0cm is installed respectively as cathode and anode, is reacted after leading to the electric current of 1.0mA
24h;
(2) it washs drying: mixture after reaction is filtered, take filtrate successively with saturation NaHCO3Solution,
Saturated salt solution and pure water carry out washing extraction, will wash after organic phase extracted is dried with anhydrous sodium sulfate and rotate
Evaporation, obtains crude product;
(3) amide compound purifies: crude product being purified by column chromatography, is formed with petroleum ether and ethyl acetate
Mixed solvent carries out gradient elution, and wherein the volume ratio of in the mixed solvent petroleum ether and ethyl acetate gradually becomes 5:1 from 10:1,
Obtain amide product III14, yield 97%.
Reactant II is being changed to thio caproic acid, methylpropanoic acid, cyclopropanecarboxylic acid, cyclohexanecarboxylic acid, benzoic acid, other reaction items
Part is constant, the yield of obtained amide product III15 is 94%, the yield of III16 is 85%, the yield of III17 is 95%,
The yield of III18 is 92% and the yield of III19 is that 95%, III14~III19 structural formula is as follows:
Embodiment 7
Application of the electrochemical oxidation synthetic method of amide in pharmaceutical chemistry synthesizes epiphysin:
The reaction route of epiphysin is as follows:
, it is 97% by the yield that the reaction obtains epiphysin, can be used in organism adjusting swashing for biological clock
Element, while treatment of insomnia patients can also be used in medicine.
A kind of mechanism study of the electrochemical oxidation synthetic method of amide:
In order to further prove amide electrochemical oxidation synthetic method mechanism, carried out a series of control experiment,
The disulfide reducing agent dithiothreitol (DTT) (DTT) of four times of equivalents, other reactions are added i.e. in the synthetic reaction system of III1
Condition is identical, cannot detect that the III1 of product is generated after reaction, while passing through cyclic voltammetry testing result such as Fig. 4 institute
Show, relative to saturation mercury electrode, thioacetic acid potassium (E in acetonitrileox=+0.33V) redox potential be lower than aniline (Eox=+
Redox potential 1.15V), therefore thioacetic acid potassium can be deduced and be preferentially oxidized anodically in a cell.
In conjunction with the relationship of amide product in above test result and embodiment and reaction condition, reactant property, thus it is speculated that
The mechanism of the electrochemical oxidation synthetic method of amide is as shown in figure 5, i.e. reactant I is oxidized anodically into freedom in electrochemical cell
Base intermediate, latter two right free radical intermediate carry out coupling and form crucial intermediate disulfide, and disulfide is again
Nucleophilic addition-elimination reaction occurs with reactant II and generates amide.
Electrochemical oxidation synthetic method of the invention prepares amide compound and does not need any catalyst, reaction condition temperature
With by-product is few, is conducive to the synthesis and purifying of amide compound, the amide compound of high yield is obtained, in pharmaceutical synthesis
In prepare amides drug and have a wide range of applications.
Finally, it is stated that preferred embodiment above is only used to illustrate the technical scheme of the present invention and not to limit it, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (10)
1. a kind of electrochemical oxidation synthetic method of amide, which is characterized in that the reaction formula of the synthetic method is as follows:
The reactant I is thiocarboxylic acid or dithionate, and the reactant II is primary amine, secondary amine, wherein R1For chain
Alkyl, naphthenic base or phenyl and its derivative, R2For H, alkyl or phenyl and its derivative, R3For H, alkyl or phenyl
And its derivative.
2. the electrochemical oxidation synthetic method of a kind of amide according to claim 1, which is characterized in that the synthetic method packet
Include following steps:
1) electrochemical oxidation: reactant I and reactant II being added in reactor first, and electrolyte, organic solvent is added and stirs
Son is mixed, two platinum plate electrodes is secondly installed in the reactor and makees to be respectively cathode and anode, galvanization carries out electrochemical oxidation
Reaction;
2) it washs drying: the mixture in step 1) after reaction in reactor is filtered, take filtrate successively with saturation
NaHCO3Solution, saturated salt solution and pure water carry out washing extraction, after washing organic phase desiccant dryness extracted
Rotary evaporation concentration is carried out, crude product is obtained;
3) amide compound purifies: crude product being purified by column chromatography, obtains amide product III.
3. a kind of electrochemical oxidation synthetic method of amide according to claim 1 or claim 2, which is characterized in that described organic molten
Agent includes any one in acetonitrile, methylene chloride, acetone, tetrahydrofuran or ethyl acetate.
4. a kind of electrochemical oxidation synthetic method of amide according to claim 1 or claim 2, which is characterized in that the electrolyte
Include tetrabutyl ammonium tetrafluoroborate, tetrabutyl ammonium hexafluorophosphate, tetrabutyl paratoluenesulfonic acid ammonium salt, tetrabutyl ammonium acetate, perchloric acid
Any one in lithium or sodium tetrafluoroborate.
5. a kind of electrochemical oxidation synthetic method of amide according to claim 1 or claim 2, which is characterized in that the platinized platinum
Specification is 1.0cm × 1.0cm, and the electric current is 1.0~12.0mA.
6. a kind of electrochemical oxidation synthetic method of amide according to claim 1 or claim 2, which is characterized in that the electrolyte
Concentration be 0.1mol/L.
7. according to a kind of electrochemical oxidation synthetic method of amide as claimed in claim 1 or 2, which is characterized in that the time of reaction is
12~for 24 hours.
8. according to a kind of electrochemical oxidation synthetic method of amide as claimed in claim 1 or 2, which is characterized in that the desiccant is
Anhydrous sodium sulfate.
9. according to a kind of electrochemical oxidation synthetic method of amide described in claim 2, which is characterized in that the elution of the column chromatography
Agent is the mixed solvent of the petroleum ether that volume ratio is 2~10:1 and ethyl acetate composition.
10. a kind of any one of the claim 1~9 electrochemical oxidation synthetic method of amide prepares amide in pharmaceutical synthesis
The application of class drug.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811457424.5A CN109321940A (en) | 2018-11-30 | 2018-11-30 | A kind of the electrochemical oxidation synthetic method and its application of amide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811457424.5A CN109321940A (en) | 2018-11-30 | 2018-11-30 | A kind of the electrochemical oxidation synthetic method and its application of amide |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109321940A true CN109321940A (en) | 2019-02-12 |
Family
ID=65255966
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811457424.5A Pending CN109321940A (en) | 2018-11-30 | 2018-11-30 | A kind of the electrochemical oxidation synthetic method and its application of amide |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109321940A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113089005A (en) * | 2021-03-01 | 2021-07-09 | 华南理工大学 | Electrochemical synthesis method of sulfamide |
CN113755862A (en) * | 2021-09-30 | 2021-12-07 | 西南大学 | Method for preparing aromatic alpha-diketone compound by electrochemical oxidation |
CN114752955A (en) * | 2022-04-20 | 2022-07-15 | 广西师范大学 | Method for electrochemically synthesizing N-nitroso-2-aminobenzophenone compound |
CN114990590A (en) * | 2022-07-15 | 2022-09-02 | 江西师范大学 | Novel method for electrocatalysis metal-free transamidation reaction |
Citations (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB721742A (en) * | 1950-02-17 | 1955-01-12 | Research Corp | Improvements in or relating to compounds having vitamin activity and methods of preparing them |
CN1032786A (en) * | 1987-09-29 | 1989-05-10 | 万有制药株式会社 | N-acyl amino acid derivative and uses thereof |
CN1105984A (en) * | 1993-06-30 | 1995-08-02 | 三共株式会社 | Amide and urea derivatives having anti-hypercholesteremic activity, their preparation and their therapeutic uses |
CN101358369A (en) * | 2007-08-02 | 2009-02-04 | 香港中文大学 | Functionalized carbon nanotube coating and use thereof |
CN101891668A (en) * | 2010-06-18 | 2010-11-24 | 西南大学 | L-prolinamide derivative, preparation method and application of same |
CN102317253A (en) * | 2009-02-24 | 2012-01-11 | 学校法人立命馆 | Both-end acid amide type hydrogel adhesive |
CN102560527A (en) * | 2012-02-22 | 2012-07-11 | 西南大学 | Direct electrochemical synthesis method of 5-nitro-1, 4-naphthoquinone |
CN102817042A (en) * | 2012-08-25 | 2012-12-12 | 太原理工大学 | Preparation method for electroactive polypyrrole film |
CN102936215A (en) * | 2012-11-09 | 2013-02-20 | 怀化学院 | Synthesizing method for 2-sulfydryl-N-(6-(3-arylurea) hexyl) amide |
CN103060837A (en) * | 2013-01-29 | 2013-04-24 | 哈尔滨理工大学 | Method for preparing 2-amino-5-bromo-N,3-dimethyl-benzamide |
CN103233246A (en) * | 2013-04-19 | 2013-08-07 | 中南大学 | Method for preparing powder material with electrochemical cathode |
CN103510104A (en) * | 2013-09-29 | 2014-01-15 | 浙江工业大学 | Method for synthesizing 2-mercaptobenzothiazole metal compound |
WO2014045293A1 (en) * | 2012-09-24 | 2014-03-27 | Krisani Bioscience (P) Ltd. | Fatty acid amides with a cysteamine or an acetylated cysteamine group and uses thereof |
US20140142332A1 (en) * | 2012-11-19 | 2014-05-22 | Technion Research & Development Foundation Limited | Process of preparing grignard reagent |
JP2014198699A (en) * | 2013-03-29 | 2014-10-23 | 山本化成株式会社 | Anthraquinone-based compound and photocurable resin composition |
CN104379814A (en) * | 2012-06-15 | 2015-02-25 | 巴斯夫欧洲公司 | Anodic oxidation of organic substrates in the presence of nucleophiles |
CN104532285A (en) * | 2014-12-12 | 2015-04-22 | 华南理工大学 | Electrochemical preparation method of 2-methyl furan |
CN104593810A (en) * | 2014-12-20 | 2015-05-06 | 中山大学 | Method for preparing tetramethylammonium hydroxide by continuous flow bioelectrochemistry system |
CN104818513A (en) * | 2014-02-04 | 2015-08-05 | 丰田自动车株式会社 | Electroplating cell, metal coating and method of forming the same |
CN105543886A (en) * | 2015-12-17 | 2016-05-04 | 浙江工业大学 | Electrochemical catalytic synthesis method of aromaticnitrile |
CN105543887A (en) * | 2015-12-31 | 2016-05-04 | 濮阳蔚林化工股份有限公司 | Electrolytic oxidation preparation method of sulfenamide accelerator |
CN106574380A (en) * | 2014-08-14 | 2017-04-19 | 巴斯夫欧洲公司 | Process for preparing alcohols by electrochemical reductive coupling |
CN107200706A (en) * | 2016-03-16 | 2017-09-26 | 中国科学院上海药物研究所 | Cyclopropylamine class compound of one class fluorine substitution and preparation method thereof, pharmaceutical composition and purposes |
EP3260577A1 (en) * | 2016-06-20 | 2017-12-27 | Panasonic Intellectual Property Management Co., Ltd. | Desorbing process, hydrogen-supplying solution, and desorbing apparatus |
CN107858700A (en) * | 2017-10-31 | 2018-03-30 | 华南理工大学 | The electrochemical method for synthesizing of the benzothiazole of 2 substitutions |
CN108505063A (en) * | 2018-04-19 | 2018-09-07 | 华南理工大学 | A kind of electrochemical preparation method of N- (3,5- dimethyl -4- hydroxy phenyls) acetamide |
CN108558692A (en) * | 2018-04-20 | 2018-09-21 | 上海工程技术大学 | A kind of preparation method of amides compound |
CN108698992A (en) * | 2016-03-18 | 2018-10-23 | 特殊治疗有限公司 | 2- cyano isoindoline derivatives for treating cancer |
-
2018
- 2018-11-30 CN CN201811457424.5A patent/CN109321940A/en active Pending
Patent Citations (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB721742A (en) * | 1950-02-17 | 1955-01-12 | Research Corp | Improvements in or relating to compounds having vitamin activity and methods of preparing them |
CN1032786A (en) * | 1987-09-29 | 1989-05-10 | 万有制药株式会社 | N-acyl amino acid derivative and uses thereof |
CN1105984A (en) * | 1993-06-30 | 1995-08-02 | 三共株式会社 | Amide and urea derivatives having anti-hypercholesteremic activity, their preparation and their therapeutic uses |
CN101358369A (en) * | 2007-08-02 | 2009-02-04 | 香港中文大学 | Functionalized carbon nanotube coating and use thereof |
CN102317253A (en) * | 2009-02-24 | 2012-01-11 | 学校法人立命馆 | Both-end acid amide type hydrogel adhesive |
CN101891668A (en) * | 2010-06-18 | 2010-11-24 | 西南大学 | L-prolinamide derivative, preparation method and application of same |
CN102560527A (en) * | 2012-02-22 | 2012-07-11 | 西南大学 | Direct electrochemical synthesis method of 5-nitro-1, 4-naphthoquinone |
CN104379814A (en) * | 2012-06-15 | 2015-02-25 | 巴斯夫欧洲公司 | Anodic oxidation of organic substrates in the presence of nucleophiles |
CN102817042A (en) * | 2012-08-25 | 2012-12-12 | 太原理工大学 | Preparation method for electroactive polypyrrole film |
WO2014045293A1 (en) * | 2012-09-24 | 2014-03-27 | Krisani Bioscience (P) Ltd. | Fatty acid amides with a cysteamine or an acetylated cysteamine group and uses thereof |
CN102936215A (en) * | 2012-11-09 | 2013-02-20 | 怀化学院 | Synthesizing method for 2-sulfydryl-N-(6-(3-arylurea) hexyl) amide |
US20140142332A1 (en) * | 2012-11-19 | 2014-05-22 | Technion Research & Development Foundation Limited | Process of preparing grignard reagent |
CN103060837A (en) * | 2013-01-29 | 2013-04-24 | 哈尔滨理工大学 | Method for preparing 2-amino-5-bromo-N,3-dimethyl-benzamide |
JP2014198699A (en) * | 2013-03-29 | 2014-10-23 | 山本化成株式会社 | Anthraquinone-based compound and photocurable resin composition |
CN103233246A (en) * | 2013-04-19 | 2013-08-07 | 中南大学 | Method for preparing powder material with electrochemical cathode |
CN103510104A (en) * | 2013-09-29 | 2014-01-15 | 浙江工业大学 | Method for synthesizing 2-mercaptobenzothiazole metal compound |
CN104818513A (en) * | 2014-02-04 | 2015-08-05 | 丰田自动车株式会社 | Electroplating cell, metal coating and method of forming the same |
CN106574380A (en) * | 2014-08-14 | 2017-04-19 | 巴斯夫欧洲公司 | Process for preparing alcohols by electrochemical reductive coupling |
CN104532285A (en) * | 2014-12-12 | 2015-04-22 | 华南理工大学 | Electrochemical preparation method of 2-methyl furan |
CN104593810A (en) * | 2014-12-20 | 2015-05-06 | 中山大学 | Method for preparing tetramethylammonium hydroxide by continuous flow bioelectrochemistry system |
CN105543886A (en) * | 2015-12-17 | 2016-05-04 | 浙江工业大学 | Electrochemical catalytic synthesis method of aromaticnitrile |
CN105543887A (en) * | 2015-12-31 | 2016-05-04 | 濮阳蔚林化工股份有限公司 | Electrolytic oxidation preparation method of sulfenamide accelerator |
CN107200706A (en) * | 2016-03-16 | 2017-09-26 | 中国科学院上海药物研究所 | Cyclopropylamine class compound of one class fluorine substitution and preparation method thereof, pharmaceutical composition and purposes |
CN108698992A (en) * | 2016-03-18 | 2018-10-23 | 特殊治疗有限公司 | 2- cyano isoindoline derivatives for treating cancer |
EP3260577A1 (en) * | 2016-06-20 | 2017-12-27 | Panasonic Intellectual Property Management Co., Ltd. | Desorbing process, hydrogen-supplying solution, and desorbing apparatus |
CN107858700A (en) * | 2017-10-31 | 2018-03-30 | 华南理工大学 | The electrochemical method for synthesizing of the benzothiazole of 2 substitutions |
CN108505063A (en) * | 2018-04-19 | 2018-09-07 | 华南理工大学 | A kind of electrochemical preparation method of N- (3,5- dimethyl -4- hydroxy phenyls) acetamide |
CN108558692A (en) * | 2018-04-20 | 2018-09-21 | 上海工程技术大学 | A kind of preparation method of amides compound |
Non-Patent Citations (8)
Title |
---|
JIANG, HUANFENG 等: ""Synthesis of Amides via Palladium-Catalyzed Amidation of Aryl Halides"", 《ORGANIC LETTERS》 * |
JIANG, YANG-YE 等: ""Electrochemical Oxidative Amination of Sodium Sulfinates: Synthesis of Sulfonamides Mediated by NH4I as a Redox Catalyst"", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
SEN LIANG 等: ""Electrochemically Oxidative α-C–H Functionalization of Ketones: A Cascade Synthesis of α-Amino Ketones Mediated by NH4I"", 《ORGANIC CHEMISTRY》 * |
ZHENG, XIAO 等: ""Titanocene(III)-Catalyzed Three-Component Reaction of Secondary Amides, Aldehydes, and Electrophilic Alkenes"", 《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》 * |
桂伟志 等: "《有机电化学合成与机理研究指南》", 31 August 1992, 天津科技翻译出版公司 * |
顾可权 等: "《有机合成化学》", 28 February 1987, 上海科学技术出版社 * |
魏献军 等: ""电化学氧化法制备偶氮二甲酰胺的研究"", 《河南师范大学学报(自然科学版)》 * |
黄昊来: ""酰胺/砜类化合物电化学合成的研究"", 《中国优秀而硕士学位沦为全文数据库 工程科技Ⅰ辑》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113089005A (en) * | 2021-03-01 | 2021-07-09 | 华南理工大学 | Electrochemical synthesis method of sulfamide |
CN113089005B (en) * | 2021-03-01 | 2022-02-15 | 华南理工大学 | Electrochemical synthesis method of sulfamide |
CN113755862A (en) * | 2021-09-30 | 2021-12-07 | 西南大学 | Method for preparing aromatic alpha-diketone compound by electrochemical oxidation |
CN114752955A (en) * | 2022-04-20 | 2022-07-15 | 广西师范大学 | Method for electrochemically synthesizing N-nitroso-2-aminobenzophenone compound |
CN114990590A (en) * | 2022-07-15 | 2022-09-02 | 江西师范大学 | Novel method for electrocatalysis metal-free transamidation reaction |
CN114990590B (en) * | 2022-07-15 | 2023-08-18 | 江西师范大学 | Novel method for electrocatalytic metal-free transamidation reaction |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109321940A (en) | A kind of the electrochemical oxidation synthetic method and its application of amide | |
von Eschwege et al. | Chemical and electrochemical oxidation and reduction of dithizone | |
CN111334817B (en) | Electrochemical synthesis method of 2-substituted benzothiazole compound | |
Shukla et al. | A comparative study of piperidinium and imidazolium based ionic liquids: thermal, spectroscopic and theoretical studies | |
CN109518212A (en) | A kind of method of disulfide of the electrochemistry formated with S -- S | |
CN101616898A (en) | Cyclic guanidine ionic liquid | |
CN112126942A (en) | Method for realizing secondary arylamine N-N coupling by using electrochemical reaction | |
Ameri et al. | Green and highly efficient synthesis of new bis-benzofurans via electrochemical methods under ECECCC mechanism | |
Kunz et al. | Unraveling the electrochemistry of verdazyl species in acidic electrolytes for the application in redox flow batteries | |
Jeon et al. | Symmetrical and unsymmetrical quadruply aza-bridged closely interspaced cofacial bis (5, 10, 15, 20-tetraphenylporphyrins). 4. Structure and conformational effects on electrochemistry and the catalysis of electrochemical reduction of dioxygen by doubly, triply, and quadruply N, N-dimethylene sulfonamide bridged dimer bis (cobalt tetraphenylporphyrins) | |
Shaaban et al. | Electrolytic partial fluorination of organic compounds. Part 56: Highly regioselective anodic mono-and difluorination of s-triazolo [3, 4-b][1, 3, 4] thiadiazine derivatives | |
Riyadh et al. | Electrolytic partial fluorination of organic compounds. Part 57: Regioselective anodic monofluorination of nitrogen-containing heterocyclic propargyl sulfides | |
Qiao et al. | Physicochemical properties of tungstate-based room-temperature ionic liquids | |
CN113402434A (en) | Novel NH-sulfoxide imine compound and synthetic method thereof | |
Oyanagi et al. | Electrochemical Properties and Fluorination of Cyclopropane Derivatives Bearing Arylthio Groups | |
Zhong et al. | Electrochemical synthesis for benzisothiazol-3 (2H)-ones by dehydrogenative NS bond formation | |
Du et al. | Reduction of 1-(2-Chloroethyl)-2-nitrobenzene and 1-(2-Bromoethyl)-2-nitrobenzene at Carbon Cathodes: Electrosynthetic Routes to 1-Nitro-2-vinylbenzene and 1H-Indole | |
Yang et al. | Synthesis of Fluorinated Amines: A Personal Account | |
Wawzonek et al. | Intermediates in the electrochemical reduction of carbon disulfide at a mercury cathode in aprotic solvents | |
Yang et al. | Electrochemical Oxidative Esterification of Thiophenols: Efficient Access to Sulfinic Esters | |
Biswas et al. | Supporting Electrolyte‐Free Electrochemical Oxidative C− H Sulfonylation and Thiocyanation of Fused Pyrimidin‐4‐Ones in an All‐Green Electrolytic System | |
Manivel et al. | Electrochemical behaviour of tetra-n-butylammonium nonaflate as an ionic liquid and as a supporting electrolyte in aprotic solvents: A comparative study | |
CN104341459A (en) | N-(4-ferrocenylphenyl)amide compounds, and synthesis method thereof application thereof | |
Bhosle et al. | Zn catalyzed a simple and convenient method for thiourea synthesis | |
Gildeh et al. | Synthesis and characterization of dicationic and monocationic fluorine-containing DBU based ionic liquids: Experimental and quantum chemical approaches |
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 | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190212 |
|
RJ01 | Rejection of invention patent application after publication |