CN108314599A - A kind of method that aldehyde or alcohol are directly translated into carboxylic acid - Google Patents
A kind of method that aldehyde or alcohol are directly translated into carboxylic acid Download PDFInfo
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- CN108314599A CN108314599A CN201810159410.9A CN201810159410A CN108314599A CN 108314599 A CN108314599 A CN 108314599A CN 201810159410 A CN201810159410 A CN 201810159410A CN 108314599 A CN108314599 A CN 108314599A
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- VUYFZUGNBKMGAJ-UTCJRWHESA-N C/C=C\c1ccccc1C(CC(O)=O)=C Chemical compound C/C=C\c1ccccc1C(CC(O)=O)=C VUYFZUGNBKMGAJ-UTCJRWHESA-N 0.000 description 1
- RRJRFNUPXQLYHX-UHFFFAOYSA-N CC(c1ccccc1)NO Chemical compound CC(c1ccccc1)NO RRJRFNUPXQLYHX-UHFFFAOYSA-N 0.000 description 1
- FNXKHOZETODZLP-UHFFFAOYSA-N Cc1ccc(cccc2CC=O)c2c1 Chemical compound Cc1ccc(cccc2CC=O)c2c1 FNXKHOZETODZLP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/08—Formation or introduction of functional groups containing oxygen of carboxyl groups or salts, halides or anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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Abstract
The invention discloses a kind of aldehyde or alcohol to aoxidize the method for being directly translated into carboxylic acid, is characterized in pure oxygen environment, under N hydroxy imide class compound for catalysis or under N hydroxy imide class compounds and nitrite compounds co-catalysis, makes CH2OH and CHO oxidations are directly translated into carboxylic acid compound.The present invention uses oxygen as oxidant, does not add any metallic catalyst, and environmental-friendly, high catalytic efficiency is easy to operate simple.It is different from previous metal catalyst system and complex catalysts system, during existing metal catalyst system, the residual of transition metal can be caused using transition metal, and the present invention is using nonmetal catalyzed system, it is environmentally protective, metal residual problem is avoided, this provides a kind of new method to solving the transition metal residue problem in pharmaceutical synthesis.
Description
Technical field
The invention belongs to oxidation catalysis CH2OH and CHO is at carboxylic acid compound technical field, and in particular to the oxygen of alcohol or aldehydes
Change the method for being directly translated into carboxylic acid.
Background technology
Carboxylic acid is widespread in nature, and has very important effect to the daily life of the mankind.FDA approveds
In the drug of listing, contain carboxylic acid structure in a large amount of drug.Such as, it is used for the brufen of rheumatism and rheumatoid arthritis, is used
The Ofloxacin of the acute and chronic infection at the positions such as respiratory tract, throat, tonsillotome caused by gram-negative bacteria, captopril, Ji
Non- Betsy, mefenamic acid etc..Carboxylic acid is also typically used as the intermediate of synthetic ester, amide and nitrile compounds.Ester, amide and
Nitrile compounds also largely exist in common drug molecule.Such as, C14H10Cl2NNaO2, piroxicam and Flecainide etc..Cause
This catalysis CH2OH and CHO is directly translated into the reaction of carboxylic acid in the fields such as laboratory, chemical industry and pharmacy extensive application.
The method of traditional synthesis of carboxylic acid is using aldehyde or alcohol and equivalent or even excessive oxidizing to react acquisition.Classical oxidation
Method has:KMnO4,CrO3,KIO4,KHSO5,NaClO2.It is efficient and it is environmental-friendly by formoxy- chemical conversion carboxylic acid be still huge
Challenge.Development in recent years uses transition metal copper or silver to be used as catalyst, adds expensive Phosphine ligands or NHC Cabbeens are matched
Body limits its large-scale application in laboratory, industry and pharmacy because of high transition metal and ligand.So far, make
Using nonmetallic as catalyst, direct oxidation catalytic alcohol or aldehyde, there is still a need for development better methods at carboxylic acid compound.
In order to solve problem above,《German applied chemistry》(Angew.Chem.Int.Ed.,2017,56,3867–3871)
A kind of method using polyoxometalates (POMs) as homogeneous catalyst proposed is to use 0.1mol%
[FeIIIMo6] be used as catalyst, the sodium carbonate of 0.1 equivalent as additive, oxygen as final oxidant, water as solvent,
8h is reacted at 50 DEG C, and aliphatic and aromatic aldehyde are oxidized to carboxylic acid.This method is although avoid equivalent or even excessive oxidation
The use of agent, but special polyoxometalates (POMs) has been used to be used as homogeneous catalyst, and can only aoxidize
Aldehyde limits the universality of this method to carboxylic acid.
Under Dutch Elsevier《Tetrahedron》(Tetrahedron, 1981,2091-2096) reports classical
Pinnick oxidation reactions, the method use sodium chlorite, sodium dihydrogen phosphate and additional 2- methyl-2-butenes as chlorine just
Ion trap agent, the tert-butyl alcohol and water, although universality is preferable, are used as solvent, energy selective oxidation aldehyde to carboxylic acid
It is uneconomical that excessive reagent causes atom.
The U.S.《Organic chemistry communicates》(Org.Lett., 2003,7,1031-1034) reports the peroxide list using equivalent
The method that formoxy- is melted into carboxylic acid by potassium sulfonate in DMF is to use the peroxide list potassium sulfonates of 1.0 equivalents as oxidant, N, N- bis-
Methylformamide reacts 3h and generates corresponding aliphatic and aromatic carboxylic acid, yield 30- at room temperature as solvent
99%.Since the method use the peroxide list potassium sulfonates of equivalent, oxidation is uneconomical, and has used boiling point higher N, N- bis-
Methylformamide is inconvenient in post-processing as solvent.
The U.S.《Organic chemistry communicates》(Org.Lett., 2016,18,3590-3593) is reported using ketoABNO and Asia
Sodium nitrate uses acetonitrile as solvent, formoxy- is melted into carboxylic acid as additive, oxygen as catalyst, nitric acid as oxidant
Method, at 23 DEG C reacting 8h generates corresponding aliphatic and aromatic carboxylic acid, yield 54-96%.Due to this method
Use special nitrogen oxides as catalyst, catalyst is not easy to obtain, and reaction system is complex, and uses nitric acid conduct
Additive exists to part functional group incompatibility problem.
The U.S.《American Chemical Society》(J.Am.Chem.Soc., 2016,138,8344-8347), which is described, a kind of using nine
As catalyst, the KCl of 0.1 equivalent is aoxidized as additive, oxygen or air as final by nitric hydrate iron and TEMPO
Agent, 1,2- dichloroethanes is as solvent, and after reacting 12-36h at room temperature, the method for converting aldehyde and alcohol to carboxylic acid, yield exists
65-99%.Since this method uses metallic iron as catalyst, to be difficult to avoid the metal residual problem in synthetic drug.
Under Dutch Elsevier《Catalysis communication》(Catalysis Communications,2016,83,82-87)
It elaborates to use n-Hydroxyphthalimide and nitrite tert-butyl as catalyst, oxygen is as oxidant, by benzyl
Firsts and seconds alcohol is oxidized into aldehyde and ketone, does not continue to be oxidized to carboxylic acid.So and unresolved economical convenient by alcohols and aldehydes
A problem of direct step is oxidized to carboxylic acid.
As it can be seen that the prior art uses metallic catalyst and equivalent or even excessive oxidant mostly, to not be avoided that
Metal residual in synthetic pharmacochemistry and uneconomical convenient problem.So using nonmetal catalyzed, oxygen is as oxidation
Agent and it is economical it is convenient be direction that future development aldehyde or alcohol are directly translated into carboxylic acid.
Invention content
The purpose of the present invention is to propose to a kind of aldehyde or alcohol to aoxidize the method for being directly translated into carboxylic acid, to overcome existing method
Drawbacks described above.
Aldehyde or alcohol of the present invention aoxidize the method for being directly translated into carboxylic acid, it is characterised in that:In oxygen atmosphere, by catalyst
N- hydroxy imide class compounds are 0.05~0.15 in molar ratio with fatty aldehyde compound:1, or by 0.1~0.2 equivalent
Catalyst n-hydroxy imide class compound, 2.0 equivalents nitrite compounds be added to the aromatic aldehyde containing 1.0 equivalents
In the solvent of class or aromatic alcohol or the 2mL of aliphatic alcohols compound, 3-48h is reacted at 30-80 DEG C, with petroleum ether/acetic acid second
Ester/dichloromethane by volume 5~2:1:1 mixing is used as eluant, eluent, column chromatography for separation to obtain product;Or directly use dichloromethane
Alkane is that extractant is extracted --- after the completion of reaction, the NaOH of a concentration of 1M is added to pH value of solution after 5mL water is first added
After the extraction three times of 5mL dichloromethane the HCl to pH=1-2 of a concentration of 1M is added, with 5mL dichloros in=13-14 in water phase
Methane extracts five times, and merging extracts five organic phases, dry with saturated common salt water washing, obtains product.
The N- hydroxy imides catalyst is selected from N- bromo-succinimides, N- hydroxyl -1,8- naphthalimides, N-
Hydroxy maleimide, N- hydroxyl -4,5,6,7- tetrachloro-phthalimides, n-hydroxysuccinimide or N- hydroxyl neighbour's benzene
Dicarboximide.
The nitrous acid ester is selected from methyl nitrite, nitrous ether (ethyl nitrite), propyl nitrite, Isopropyl Nitrite, nitrous acid
Butyl ester, isoamyl nitrite, nitrite tert-butyl or nitrous acid benzyl ester.
The aldehyde-containing type and alcohol compound are selected from n-hexyl aldehyde, n-Heptaldehyde, lauric aldehyde, 2 methyl propanal, trimethyl second
Aldehyde, 2- ethyl hexanals, 2 methyl butyraldehyde, 3,3- dimethyl -1- butyraldehyde, 2- ethyl butyraldehydes, cyclopenta formaldehyde, hexahydrobenzaldehyde,
3- cyclohexyl propionic aldehyde, 6- chlorine hexanal, 5- bromines valeral, 6- (tert-butoxy amino) hexanal, 3- benzoyls propionic aldehyde, benzenpropanal, benzene second
The bromo- 1- propyl alcohol of aldehyde, 1- naphthylacetaldehydes, 2- hydrocinnamicaldehydes, para-methoxybenzyl alcohol, benzylalcohol, 3-, P-methoxybenzal-dehyde, 2- naphthaldehydes,
Benzaldehyde or 4-chloro-benzaldehyde.
The solvent is selected from dimethyl sulfoxide (DMSO), N,N-dimethylformamide, acetonitrile, benzonitrile, chlorobenzene, toluene or 1,2- bis-
Chloroethanes.
Aldehyde or alcohol of the present invention aoxidize the method for being directly translated into carboxylic acid, and N- hydroxy imide class catalyst is used due to taking
It is catalyzed aldehyde and alcohol class compound, or is cooperateed with using nitrous acid ester as radical initiator and using N- hydroxy imides and nitrous acid ester
Catalyst system and catalyzing, using oxygen as oxidant, oxidation catalysis CH2OH and CHO is converted to carboxylic acid compound, after reaction with oil
Ether/ethyl acetate/dichloromethane by volume 5~2:1:1 mixing is used as eluant, eluent, column chromatography for separation to obtain target product, or
The use of dichloromethane is directly that extractant is extracted --- after the completion of reaction, a concentration of 1M is added after 5mL water first is added
NaOH to pH value of solution=13-14, with 5mL dichloromethane extraction three times after, the HCl to pH=of a concentration of 1M is added in water phase
1-2 is extracted five times with 5mL dichloromethane, and merging extracts five organic phases, dry with saturated common salt water washing, obtains product.
The present invention is easy to operate simple, using oxygen as oxidant, does not add any metallic catalyst, environmental-friendly, catalytic efficiency
It is high.It is different from previous metal catalyst system and complex catalysts system, during existing metal catalyst system, used
The residual of transition metal can be caused by crossing metal, and the present invention is using nonmetal catalyzed system, environmentally protective, this avoid
Metal residual problem, this provides a kind of new method to solving the transition metal residue problem in pharmaceutical synthesis.
Specific implementation mode
Embodiment 1:N-caproic acidSynthesis
5mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen atmosphere
Acetonitrile 2mL is sequentially added under enclosing, 1.0 equivalent of n-hexyl aldehyde connects an oxygen ball, and oil is put into after adding glass stopper on reaction tube
In bath, 30 DEG C of reaction 3h.It after the completion of reaction, is concentrated under reduced pressure, column chromatography for separation, eluant, eluent is petrol ether/ethyl acetate/dichloro
Methane (v:v:V=2:1:1) n-caproic acid, is obtained.Yield>99%, colourless liquid;1HNMR(400MHz,CDCl3)δ2.36(t,J
=7.2Hz, 2H), 1.65-1.61 (m, 2H), 1.34-1.30 (m, 4H), 0.91-0.88 (m, 3H)13C NMR(100MHz,
CDCl3)δ180.67,34.07,31.18,24.33,22.26,13.81.
Embodiment 2:Positive enanthic acidSynthesis
5mol%NHPI is added in 25mLSchlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen atmosphere
Acetonitrile 2mL is sequentially added under enclosing, 1.0 equivalent of n-Heptaldehyde connects an oxygen ball, and oil is put into after adding glass stopper on reaction tube
In bath, 30 DEG C of reaction 3h.It after the completion of reaction, is concentrated under reduced pressure, column chromatography for separation, eluant, eluent is petrol ether/ethyl acetate/dichloro
Methane (v:v:V=5:1:1) positive enanthic acid, is obtained.Yield 93%, colourless liquid;1HNMR(400MHz,CDCl3) δ 2.36 (t, J=
7.6Hz, 2H), 1.64 (t, J=7.2Hz, 2H), 1.25-1.35 (m, 6H), 0.88 (t, J=6.8Hz, 3H)13CNMR
(100MHz,CDCl3)δ180.91,34.46,31.75,29.05,24.96,22.78,14.32.
Embodiment 3:Lauric acid n-C11H23CHO→n-C11H23The synthesis of COOH
5mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen atmosphere
Acetonitrile 2mL is sequentially added under enclosing, 1.0 equivalent of lauryl aldehyde connects an oxygen ball, and oil is put into after adding glass stopper on reaction tube
In bath, 30 DEG C of reaction 3h.It after the completion of reaction, is concentrated under reduced pressure, column chromatography for separation, eluant, eluent is petrol ether/ethyl acetate/dichloro
Methane (v:v:V=5:1:1) lauric acid, is obtained.Yield 90%, solid;1H NMR(400MHz,CDCl3) δ 2.36 (t, J=
7.6Hz, 2H), 1.66-1.59 (m, 2H), 1.29 (s, 16H), 0.895 (t, J=6.4Hz, 3H)13C NMR(100MHz,
CDCl3) δ 180.73,34.43,32.25,29.94,29.77,29.67,29.57,29.40,25.01,23.02,14.44.
Embodiment 4:2 Methylpropionic acidSynthesis
5mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen atmosphere
Acetonitrile 2mL is sequentially added under enclosing, 1.0 equivalent of 2 methyl propanal connects an oxygen ball, is put after adding glass stopper on reaction tube
Enter in oil bath pan, 30 DEG C of reaction 3h.After the completion of reaction, be concentrated under reduced pressure, column chromatography for separation, eluant, eluent be petrol ether/ethyl acetate/
Dichloromethane (v:v:V=5:1:1) 2 Methylpropionic acid, is obtained.Yield>99%, colourless liquid;1H NMR(400MHz,CDCl3)
1.19 (d, J=7.0Hz, 6H), 2.59 (m, 1H)13C NMR(100MHz,CDCl3)184.24,34.21,19.04.
Embodiment 5:Trimethylace tonitricSynthesis
10mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen
Acetonitrile 2mL is sequentially added under atmosphere, 1.0 equivalent of trimethyl-acetaldehyde connects an oxygen ball, plus after glass stopper on reaction tube
It is put into oil bath pan, 30 DEG C of reaction 3h.It after the completion of reaction, is concentrated under reduced pressure, column chromatography for separation, eluant, eluent is petroleum ether/acetic acid second
Ester/dichloromethane (v:v:V=5:1:1) trimethylace tonitric, is obtained.Yield 91%, colourless liquid;1H NMR(400MHz,
CDCl3)δ1.25(s,9H).
Embodiment 6:2- ethyl hexanalsSynthesis
15mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen
1.0 equivalent of acetonitrile 2mL, 2- ethyl hexanal is sequentially added under atmosphere, connects an oxygen ball, plus after glass stopper on reaction tube
It is put into oil bath pan, 30 DEG C of reaction 3h.It after the completion of reaction, is concentrated under reduced pressure, column chromatography for separation, eluant, eluent is petroleum ether/acetic acid second
Ester/dichloromethane (v:v:V=5:1:1) 2 ethyl hexanoic acid, is obtained.Yield 87%, colourless liquid;1H NMR(400MHz,
CDCl3) (m, the 6H) of δ 2.31-2.24 (m, 1H), 1.68-1.44 (m, 4H), 1.31 (t, J=20Hz, 4H), 0.96-0.9113C
NMR(100MHz,CDCl3)δ183.48,47.46,31.79,29.85,25.50,22.96,14.24,12.08.
Embodiment 7:2-Methyl Butyric AcidSynthesis
5mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen atmosphere
Acetonitrile 2mL is sequentially added under enclosing, 1.0 equivalent of 2 methyl butyraldehyde connects an oxygen ball, is put after adding glass stopper on reaction tube
Enter in oil bath pan, 30 DEG C of reaction 3h.After the completion of reaction, be concentrated under reduced pressure, column chromatography for separation, eluant, eluent be petrol ether/ethyl acetate/
Dichloromethane (v:v:V=5:1:1) 2-Methyl Butyric Acid, is obtained.Yield 88%, colourless liquid;1H NMR(400MHz,CDCl3)δ
2.43-2.34 (m, 1H), 1.75-1.65 (m, 1H), 1.54-1.44 (m, 1H), 1.15 (m, 3H), 0.95 (t, J=7.2Hz,
3H).13C NMR(100MHz,CDCl3)δ183.96,41.25,26.84,16.64,11.83.
Embodiment 8:3,3- dimethyl -1- butyric acidSynthesis
5mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen atmosphere
Acetonitrile 2mL is sequentially added under enclosing, 3,3- dimethyl -1- butyraldehyde, 1.0 equivalent connects an oxygen ball, and glass is added on reaction tube
It is put into oil bath pan after glass plug, 30 DEG C of reaction 3h.After the completion of reaction, be concentrated under reduced pressure, column chromatography for separation, eluant, eluent be petroleum ether/
Ethyl acetate/dichloromethane (v:v:V=5:1:1) 3,3- dimethyl -1- butyric acid, is obtained.Yield 83%, colourless liquid;1H
NMR(400MHz,CDCl3)δ2.23(s,2H),1.05(s,9H),13C NMR(100MHz,CDCl3)δ178.83,48.03,
30.97,29.21.
Embodiment 9:2 Ethylbutanoic acidSynthesis
5mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen atmosphere
1.0 equivalent of acetonitrile 2mL, 2- ethyl butyraldehyde is sequentially added under enclosing, connects an oxygen ball, is put after adding glass stopper on reaction tube
Enter in oil bath pan, 30 DEG C of reaction 3h.After the completion of reaction, be concentrated under reduced pressure, column chromatography for separation, eluant, eluent be petrol ether/ethyl acetate/
Dichloromethane (v:v:V=5:1:1) 2 Ethylbutanoic acid, is obtained.Yield 88%, weak yellow liquid;1H NMR(400MHz,CDCl3)
δ 2.24-2.18 (m, 1H), 1.69-1.48 (m, 4H), 0.94 (t, J=7.6Hz 6H),13C NMR(100MHz,CDCl3)δ
183.22,49.02,25.06,12.06.
Embodiment 10:Ring valeric acidSynthesis
5mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen atmosphere
Acetonitrile 2mL is sequentially added under enclosing, 1.0 equivalent of cyclopenta formaldehyde connects an oxygen ball, is put after adding glass stopper on reaction tube
Enter in oil bath pan, 30 DEG C of reaction 3h.After the completion of reaction, be concentrated under reduced pressure, column chromatography for separation, eluant, eluent be petrol ether/ethyl acetate/
Dichloromethane (v:v:V=2:1:1) ring valeric acid, is obtained.Yield 84%, yellow liquid;1H NMR(400MHz,CDCl3)δ2.79–
2.71(m,1H),1.93–1.79(m,4H),1.74–1.66(m,2H),1.62–1.57(m,2H).13C NMR(100MHz,
CDCl3)δ183.95,44.04,30.26,26.14.
Embodiment 11:Cyclohexanecarboxylic acidSynthesis
5mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen atmosphere
Acetonitrile 2mL is sequentially added under enclosing, 1.0 equivalent of cyclohexyl formaldehyde connects an oxygen ball, plus after glass stopper on reaction tube
It is put into oil bath pan, 30 DEG C of reaction 5h.It after the completion of reaction, is concentrated under reduced pressure, column chromatography for separation, eluant, eluent is petroleum ether/acetic acid second
Ester/dichloromethane (v:v:V=5:1:1) cyclohexanecarboxylic acid, is obtained.Yield 99%, colourless liquid;1H NMR(400MHz,CDCl3)δ
2.37–2.30(m,1H),1.95–1.92(m,2H),1.77–1.74(m,2H),1.66–1.64(m,1H),1.49–1.41(m,
2H),1.33–1.21(m,3H).13C NMR(100MHz,CDCl3)δ183.00,43.26,29.09,26.01,25.65.
Embodiment 12:3- cyclohexylpropionic acidsSynthesis
5mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen atmosphere
1.0 equivalent of acetonitrile 2mL, 3- cyclohexyl propionic aldehyde is sequentially added under enclosing, connects an oxygen ball, plus after glass stopper on reaction tube
It is put into oil bath pan, 30 DEG C of reaction 3h.It after the completion of reaction, is concentrated under reduced pressure, column chromatography for separation, eluant, eluent is petroleum ether/acetic acid second
Ester/dichloromethane (v:v:V=3:1:1) 3- cyclohexylpropionic acids, are obtained.Yield 86%, yellow liquid;1H NMR(400MHz,
CDCl3) δ 2.37 (t, J=7.6Hz, 2H), 1.74-1.62 (m, 5H), 1.55 (q, J=7.2Hz, 2H), 1.26-1.14 (m,
4H),0.93–0.84(m,4H).13C NMR(100MHz,CDCl3)δ181.26,37.42,33.23,32.36,32.04,
26.80,26.49.
Embodiment 13:
6- chlorine caproic acidsSynthesis
15mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen
1.0 equivalent of acetonitrile 2mL, 6- chlorine hexanal is sequentially added under atmosphere, connects an oxygen ball, is put after adding glass stopper on reaction tube
Enter in oil bath pan, 30 DEG C of reaction 3h.After the completion of reaction, be concentrated under reduced pressure, column chromatography for separation, eluant, eluent be petrol ether/ethyl acetate/
Dichloromethane (v:v:V=5:1:1) 6- chlorine caproic acids, are obtained.Yield 81%, colourless liquid;1H NMR(400MHz,CDCl3)δ
3.55 (t, J=6.4Hz, 2H), 2.39 (t, J=7.6Hz, 2H), 1.83-7.75 (m, 2H), 1.68-1.62 (m, 2H), 1.53-
1.47(m,2H),13C NMR(100MHz,CDCl3)δ180.06,45.05,34.14,32.51,26.61,24.22.
Embodiment 14:
5- bromine valeric acidsSynthesis
5mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen atmosphere
1.0 equivalent of acetonitrile 2mL, 5- bromine valeral is sequentially added under enclosing, connects an oxygen ball, is put into after adding glass stopper on reaction tube
In oil bath pan, 30 DEG C of reaction 6h.It after the completion of reaction, is concentrated under reduced pressure, column chromatography for separation, eluant, eluent is petrol ether/ethyl acetate/bis-
Chloromethanes (v:v:V=5:1:1) 5- bromine valeric acids, are obtained.Yield 95%, colorless solid;1HNMR(400MHz,CDCl3)δ3.43
(t, J=6.4Hz, 2H), 2.42 (t, J=7.2Hz, 2H), 1.94-1.89 (m, 2H), 1.83-1.77 (m, 2H)13C NMR
(100MHz,CDCl3)δ179.92,33.362,33.20,32.15,23.51.
Embodiment 15:
6- (tert-butoxy amino) caproic acid
Synthesis
10mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen
1.0 equivalent of acetonitrile 2mL, 6- (tert-butoxy amino) hexanal is sequentially added under atmosphere, connects an oxygen ball, is added on reaction tube
It is put into oil bath pan after upper glass stopper, 50 DEG C of reaction 3h.After the completion of reaction, it is concentrated under reduced pressure, column chromatography for separation, eluant, eluent is oil
Ether/ethyl acetate/dichloromethane (v:v:V=3:1:1) 6- (tert-butoxy amino) caproic acid, is obtained.Yield 92%, solid;1H
NMR(400MHz,CDCl3) δ 3.10-3.05 (m, 2H), 2.33 (t, J=7.2Hz, 2H), 1.66-1.59 (m, 2H), 1.53-
1.32(m,11H),1.25–1.21(m,2H).
Embodiment 16:
3- benzoylamino propionic acidsSynthesis
10mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen
1.0 equivalent of acetonitrile 2mL, 3- benzoyl propionic aldehyde is sequentially added under atmosphere, connects an oxygen ball, and glass stopper is added on reaction tube
After be put into oil bath pan, 30 DEG C reaction 3h.It after the completion of reaction, is concentrated under reduced pressure, column chromatography for separation, eluant, eluent is petroleum ether/acetic acid
Ethyl ester/dichloromethane (v:v:V=2:1:1) 3- benzoylamino propionic acids, are obtained.Yield 91%, white solid;1H NMR(400MHz,
CDCl3) δ 7.99 (d, J=7.6Hz, 2H), 7.59 (t, J=7.2Hz, 1H), 7.49 (t, J=7.6Hz, 1H), 3.33 (t, J=
6.4Hz, 2H), 2.83 (t, J=6.8Hz, 2H)13C NMR(100MHz,CDCl3)δ198.21,178.75,136.73,
133.69,129.00,128.39,33.51,28.32.
Embodiment 17:
Benzenpropanoic acidSynthesis
10mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen
Acetonitrile 2mL is sequentially added under atmosphere, 1.0 equivalent of benzenpropanal connects an oxygen ball, is put into after adding glass stopper on reaction tube
In oil bath pan, 30 DEG C of reaction 3h.It after the completion of reaction, is concentrated under reduced pressure, column chromatography for separation, eluant, eluent is petrol ether/ethyl acetate/bis-
Chloromethanes (v:v:V=5:1:1) benzenpropanoic acid, is obtained.Yield 91%, white solid;1H NMR(400MHz,CDCl3)δ7.33–
7.29 (m, 2H), δ 7.21-7.29 (m, 3H), 2.99 (t, J=7.6Hz, 2H), 2.72 (t, J=8.0Hz, 1H)13C NMR
(100MHz,CDCl3)δ179.49,140.49,128.91,128.60,126.73,35.92,30.91.
Embodiment 18:
Phenylacetic acidSynthesis
10mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen
Acetonitrile 2mL is sequentially added under atmosphere, 1.0 equivalent of phenylacetaldehyde connects an oxygen ball, is put into after adding glass stopper on reaction tube
In oil bath pan, 30 DEG C of reaction 5h.It after the completion of reaction, is concentrated under reduced pressure, column chromatography for separation, eluant, eluent is petrol ether/ethyl acetate/bis-
Chloromethanes (v:v:V=5:1:1) phenylacetic acid, is obtained.Yield 82%, faint yellow solid;1H NMR(400MHz,CDCl3)δ7.36–
7.28(m,5H),3.66(s,2H).13C NMR(100MHz,CDCl3)δ178.31,133.58,129.72,129.00,
127.71,41.39.
Embodiment 19:
1- methyl α-naphthyl acetatesSynthesis
5mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen atmosphere
1.0 equivalent of acetonitrile 2mL, 1- naphthylacetaldehyde is sequentially added under enclosing, connects an oxygen ball, is put into after adding glass stopper on reaction tube
In oil bath pan, 60 DEG C of reaction 3h.It after the completion of reaction, is concentrated under reduced pressure, column chromatography for separation, eluant, eluent is petrol ether/ethyl acetate/bis-
Chloromethanes (v:v:V=4:1:1) 1- methyl α-naphthyl acetates, are obtained.Yield 87%, solid;1H NMR(400MHz,CDCl3)δ7.95(d,J
=8Hz, 1H), 7.86 (d, J=7.6Hz, 1H), 7.84 (d, J=7.6Hz, 1H), 7.51-7.47 (m, 2H), 7.41-7.39
(m,2H),4.06(s,2H).13C NMR(100MHz,CDCl3)δ178.20,134.12,132.32,130.07,129.11,
128.70,128.55,126.84,126.21,125.79,124.01,39.11.
Embodiment 20:
2- phenylpropionic acidsSynthesis
10mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen
1.0 equivalent of acetonitrile 2mL, 2- hydrocinnamicaldehyde is sequentially added under atmosphere, connects an oxygen ball, plus after glass stopper on reaction tube
It is put into oil bath pan, 50 DEG C of reaction 10h.It after the completion of reaction, is concentrated under reduced pressure, column chromatography for separation, eluant, eluent is petroleum ether/acetic acid second
Ester/dichloromethane (v:v:V=5:1:1) 2- phenylpropionic acids, are obtained.Yield 91%, colourless liquid;1H NMR(400MHz,
CDCl3)δ7.35–7.29(m,5H),δ3.78–3.74(m,1H),δ1.55–1.52(m,3H).13C NMR(100MHz,CDCl3)
δ181.44,140.05,129.02,127.94,127.74,45.70,18.39.
Embodiment 21:
P-methoxybenzoic acidSynthesis
15mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen
Acetonitrile 2mL, 1.0 equivalent of para-methoxybenzyl alcohol are sequentially added under atmosphere, 2.0 equivalent of nitrite tert-butyl connects an oxygen ball,
Plus being put into oil bath pan after glass stopper on reaction tube, 80 DEG C are reacted 48h.After the completion of reaction, added after 5mL water first is added
Three times with the extraction of 5mL dichloromethane the HCl of a concentration of 1M is added in a concentration of 1M NaOH to pH value of solution=13-14 in water phase
It to pH value of solution=1-2, is extracted five times with 5mL dichloromethane, merges organic phase, it is dry with saturated common salt water washing, it obtains to first
P-methoxybenzoic acid.Yield 57%, faint yellow solid;1H NMR(400MHz,CDCl3) δ 8.08 (d, J=8.8Hz, 2H), 6.90
(d, J=8.8Hz, 2H), δ 3.88 (s, 3H)13C NMR(100MHz,CDCl3)δ171.90,164.39,132.71,121.95,
114.09,55.83.
Embodiment 22:
The synthesis of 3- bromo-propionic acids
15mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen
Bromo- 1.0 equivalent of 1- propyl alcohol of acetonitrile 2mL, 3- is sequentially added under atmosphere, 2.0 equivalent of nitrite tert-butyl connects an oxygen ball,
Plus being put into oil bath pan after glass stopper on reaction tube, 80 DEG C are reacted 48h.After the completion of reaction, added after 5mL water first is added
Three times with the extraction of 5mL dichloromethane the HCl of a concentration of 1M is added in a concentration of 1M NaOH to pH value of solution=13-14 in water phase
It to pH value of solution=1-2, is extracted five times with 5mL dichloromethane, merges organic phase and be dried to obtain 3- bromines with saturated common salt water washing
Propionic acid.Yield 20%, hazel-color solid;1H NMR(400MHz,CDCl3) δ 10.95 (br, 1H), 3.57 (t, J=6.8Hz,
3H), δ 2.99 (t, J=6.8Hz, 3H)13C NMR(100MHz,CDCl3)δ177.17,37.78,25.33.
Embodiment 23:
P-methoxybenzoic acidSynthesis
10mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen
Acetonitrile 2mL, 1.0 equivalent of P-methoxybenzal-dehyde are sequentially added under atmosphere, 2.0 equivalent of nitrite tert-butyl connects an oxygen
Ball, plus being put into oil bath pan after glass stopper on reaction tube, 80 DEG C are reacted 48h.After the completion of reaction, first it is added after 5mL water again
A concentration of 1M NaOH to pH value of solution=13-14 are added, three times with the extraction of 5mL dichloromethane, are added a concentration of 1M's in water phase
HCl to pH value of solution=1-2 is extracted five times with 5mL dichloromethane, merges organic phase, with saturated common salt water washing, is dried to obtain pair
Methoxy benzoic acid.Yield 63%, faint yellow solid;1H NMR(400MHz,CDCl3) δ 8.08 (d, J=8.8Hz, 2H), 6.90
(d, J=8.8Hz, 2H), δ 3.88 (s, 3H)13C NMR(100MHz,CDCl3)δ171.90,164.39,132.71,121.95,
114.09,55.83.
Embodiment 24:
2- naphthoic acidsSynthesis
20mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen
1.0 equivalent of acetonitrile 2mL, 2- naphthaldehyde is sequentially added under atmosphere, 2.0 equivalent of nitrite tert-butyl connects an oxygen ball, anti-
It should manage plus being put into oil bath pan after glass stopper, 80 DEG C are reacted 48h.After the completion of reaction, concentration is added after 5mL water first is added
For 1M NaOH to pH value of solution=13-14, three times with the extraction of 5mL dichloromethane, the HCl of a concentration of 1M is added in water phase to molten
Liquid pH=1-2 is extracted five times with 5mL dichloromethane, merges organic phase, dry with saturated common salt water washing, obtains 2- naphthalene first
Acid.Yield 82%, hazel-color solid;1H NMR(400MHz,CDCl3) δ 8.73 (s, 1H), δ 8.15 (d, J=8.4Hz, 1H), δ
8.01 (d, J=8.0Hz, 1H), 7.94-7.90 (m, 2H), 7.65-7.55 (m, 2H)13C NMR(100MHz,CDCl3)δ
172.63,136.32,132.77,132.54,129.91,129.04,128.69,128.17,127.14,126.83,125.72.
Embodiment 25:
IndomethacinSynthesis
15mol%NHPI is added in 25mL Schlenk reaction tubes, is dried in vacuo 15 minutes, oxygen is blasted, in oxygen
Acetonitrile 2mL is sequentially added under atmosphere, 1.0 equivalent of substrate aldehyde connects an oxygen ball, is put into after adding glass stopper on reaction tube
In oil bath pan, 80 DEG C of reaction 30h.After the completion of reaction, be concentrated under reduced pressure, column chromatography for separation, eluant, eluent be petrol ether/ethyl acetate/
Dichloromethane (v:V=2:1:1) Indomethacin, is obtained.Yield 91%, brown solid;1HNMR(400MHz,CDCl3)δ7.67
(d, J=8.4Hz, 2H), 7.47 (d, J=8.0Hz, 2H), 6.94 (m, 1H), 6.86 (d, J=8.8Hz, 1H), 6.68 (d, J=
12Hz,1H),3.82(s,3H),3.69(s,2H),2.38(s,3H).13C NMR(100MHz,CDCl3)δ176.53,168.65,
156.42,139.70,136.59,134.14,131.53,131.13,130.80,129.49,115.35,112.17,112.04,
101.58,56.07,30.26,13.63.
The present invention using N- hydroxy imides catalyst or with nitrous acid ester concerted catalysis aldehyde alcohol compound, take
CH2OH and CHO direct oxidations are catalytically converted into carboxylic acid compound.By above-described embodiment to aliphatic aldehyde alcohol and aromatic series aldehyde alcohol
Direct oxidation be converted to a series of experiments of the different substrates cited by carboxylic acid, can conclude and obtain:For aliphatic category bottom
Object optimum condition is n-Hydroxyphthalimide 5-15mol%, need not add nitrite tert-butyl, fatty aldehyde 1.0 is worked as
Amount, oxygen, 30-80 DEG C of reaction 3-30h;It is N- hydroxyl neighbour's benzene for aromatic series aldehyde alcohol and aliphatic alcohols substrate optimum condition
Dicarboximide 10-20mol%, 2.0 equivalent of nitrite tert-butyl, 1.0 equivalent of aromatic aldehyde, oxygen, 80 DEG C of reaction 48h.This hair
It is bright using nonmetallic catalyst system and catalyzing, N- hydroxy imide class catalyst aldehyde and alcohol class compounds have been used, with nitrous acid
Ester is radical initiator and is made using oxygen as oxidant using N- hydroxy imides and nitrous acid ester concerted catalysis system
CH2OH and CHO is converted to carboxylic acid compound, after reaction with petrol ether/ethyl acetate/dichloromethane by volume 5~2:
1:1 mixing is used as eluant, eluent, column chromatography for separation to obtain product, or directly extracted for extractant using dichloromethane ---
After reaction, the NaOH to pH value of solution=13-14 that a concentration of 1M is first added after addition 5mL water, is extracted with 5mL dichloromethane
After three times, the HCl to pH=1-2 of a concentration of 1M is added in water phase, three times with the extraction of 5mL dichloromethane, merges extraction five times
Organic phase, it is dry with saturated common salt water washing, obtain product.The above embodiment illustrates that the substrate of the present invention is generally fitted
Answering property is good, and aliphatic aromatic can realize conversion.The prior art uses metallic catalyst and equivalent or even excess mostly
Oxidant, be accordingly difficult to avoid the metal residual in synthetic drug.The present invention is easy to operate simple, using oxygen as finally
Oxidant source does not add any metallic catalyst, environmental-friendly, high catalytic efficiency.With previous metal catalyst system and
Complex catalysts system is different, and during existing metal catalyst system, the residual of transition metal can be caused using transition metal,
And the present invention is using nonmetal catalyzed system, environmentally protective, this avoid metal residual problems, this is to solving in drug
Transition metal residue problem in synthesis provides a kind of new method.
Claims (5)
1. a kind of method that aldehyde or alcohol are directly translated into carboxylic acid, it is characterised in that:In pure oxygen environment, by catalyst n-hydroxyl acyl
Imine compound is 0.05~0.15 in molar ratio with fatty aldehyde compound:1, or by the catalyst n-of 0.1~0.2 equivalent
Hydroxy imide class compound, 2.0 equivalents nitrite compounds be added to aromatic aldehydes or fragrance containing 1.0 equivalents
In the solvent of alcohols or the 2mL of aliphatic alcohols compound, 3-48h is reacted at 30-80 DEG C, with petrol ether/ethyl acetate/dichloromethane
Alkane by volume 5~2:1:1 mixing is used as eluant, eluent, column chromatography for separation to obtain product;Or it is extractant directly to use dichloromethane
Extracted --- after the completion of reaction, the NaOH to pH value of solution=13-14 of a concentration of 1M is first added after addition 5mL water, is used
After the extraction three times of 5mL dichloromethane, the HCl to pH=1-2 of a concentration of 1M is added in water phase, five are extracted with 5mL dichloromethane
Secondary, merging extracts five organic phases, dry with saturated common salt water washing, obtains product.
2. the method that aldehyde as described in claim 1 or alcohol are directly translated into carboxylic acid is characterized in that the catalyst n-hydroxyl acyl is sub-
Aminated compounds is N- bromo-succinimides, N- hydroxyl -1,8- naphthalimides, N- hydroxy maleimides, N- hydroxyls -
4,5,6,7- tetrachloro-phthalimides, n-hydroxysuccinimide or n-Hydroxyphthalimide.
3. the method that aldehyde as described in claim 1 or alcohol are directly translated into carboxylic acid is characterized in that the nitrite compounds
For methyl nitrite, nitrous ether (ethyl nitrite), propyl nitrite, Isopropyl Nitrite, butyl nitrite, isoamyl nitrite, nitrous
Tert-butyl acrylate or nitrous acid benzyl ester.
4. the method that aldehyde as described in claim 1 or alcohol are directly translated into carboxylic acid is characterized in that the aldehyde and alcohol compound are
N-hexyl aldehyde, n-Heptaldehyde, lauric aldehyde, 2 methyl propanal, trimethyl-acetaldehyde, 2- ethyl hexanals, 2 methyl butyraldehyde, 3,3- dimethyl-
1- butyraldehyde, 2- ethyl butyraldehydes, cyclopenta formaldehyde, hexahydrobenzaldehyde, 3- cyclohexyl propionic aldehyde, 6- chlorine hexanal, 5- bromines valeral, 6- (uncles
Amino butoxy) hexanal, 3- benzoyls propionic aldehyde, benzenpropanal, phenylacetaldehyde, 1- naphthylacetaldehydes, 2- hydrocinnamicaldehydes, para-methoxybenzyl alcohol,
The bromo- 1- propyl alcohol of benzylalcohol, 3-, P-methoxybenzal-dehyde, 2- naphthaldehydes, benzaldehyde or 4-chloro-benzaldehyde.
5. the method that aldehyde as described in claim 1 or alcohol are directly translated into carboxylic acid, be characterized in that the solvent be dimethyl sulfoxide (DMSO),
N,N-dimethylformamide, acetonitrile, benzonitrile, chlorobenzene, toluene or 1,2- dichloroethanes.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020140675A1 (en) * | 2019-01-03 | 2020-07-09 | 中国科学院大连化学物理研究所 | Preparation method for 2,5-furan diacarboxylic acid |
CN111620806A (en) * | 2020-06-12 | 2020-09-04 | 史卫明 | Preparation method of amlodipine intermediate |
CN112409144A (en) * | 2019-08-22 | 2021-02-26 | 浙江大学 | Method for synthesizing carboxylic acid or ketone compound from alcohol or aldehyde by using oxygen or oxygen in air as oxidant |
CN113680306A (en) * | 2021-09-13 | 2021-11-23 | 盐城市春竹香料有限公司 | Device and method for preparing 2-methylbutyric acid by continuously oxidizing 2-methylbutyraldehyde |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090075203A1 (en) * | 2003-10-01 | 2009-03-19 | Shenggao Liu | Photoresist compositions comprising diamondoid derivatives |
-
2018
- 2018-02-26 CN CN201810159410.9A patent/CN108314599A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090075203A1 (en) * | 2003-10-01 | 2009-03-19 | Shenggao Liu | Photoresist compositions comprising diamondoid derivatives |
Non-Patent Citations (4)
Title |
---|
FRANCESCO MINISCI ET AL,: "Molecule-induced homolysis of N-hydroxyphthalimide(NHPI) by peracids and dioxirane. A new, simple, selective aerobic radical epoxidation of alkenes", 《TETRAHEDRON LETTERS》 * |
FRANCESCO MINISCI ETAL: ""Molecule-induced homolysis of N-hydroxyphthalimide(NHPI)by peracids and dioxirane.A new, simple, selective aerobic radical epoxidation of alkenes", 《TETRAHEDRON LETTERS》 * |
YASUTAKA ISHII ET AL: "A Novel Catalysis of N-Hydroxyphthalimide in the Oxidation of Organic Substrates by Molecular Oxygen", 《J.ORG.CHEM》 * |
YONGKE HU: "NHPI/tert-butyl nitrite:A highly efficient metal-free catalytic system for aerobic oxidation of alcohols to carbonyl compounds using molecular oxygen as the terminal oxidant", 《CATALYSIS COMMUNICATIONS》 * |
Cited By (6)
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WO2020140675A1 (en) * | 2019-01-03 | 2020-07-09 | 中国科学院大连化学物理研究所 | Preparation method for 2,5-furan diacarboxylic acid |
CN112409144A (en) * | 2019-08-22 | 2021-02-26 | 浙江大学 | Method for synthesizing carboxylic acid or ketone compound from alcohol or aldehyde by using oxygen or oxygen in air as oxidant |
CN112409144B (en) * | 2019-08-22 | 2022-10-28 | 浙江大学 | Method for synthesizing carboxylic acid or ketone compound from alcohol or aldehyde by using oxygen or oxygen in air as oxidant |
CN111620806A (en) * | 2020-06-12 | 2020-09-04 | 史卫明 | Preparation method of amlodipine intermediate |
CN111620806B (en) * | 2020-06-12 | 2021-05-11 | 常州瑞明药业有限公司 | Preparation method of amlodipine intermediate |
CN113680306A (en) * | 2021-09-13 | 2021-11-23 | 盐城市春竹香料有限公司 | Device and method for preparing 2-methylbutyric acid by continuously oxidizing 2-methylbutyraldehyde |
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