CN108383710A - A kind of method that Anderson types polyacid catalysis oxidation prepares benzoic acid - Google Patents
A kind of method that Anderson types polyacid catalysis oxidation prepares benzoic acid Download PDFInfo
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- CN108383710A CN108383710A CN201810191830.5A CN201810191830A CN108383710A CN 108383710 A CN108383710 A CN 108383710A CN 201810191830 A CN201810191830 A CN 201810191830A CN 108383710 A CN108383710 A CN 108383710A
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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
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/881—Molybdenum and iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a kind of methods that Anderson types polyacid catalysis oxidation prepares benzoic acid.It is as follows：1) by toluene under catalyst, oxidant and Additive, occur oxidation reaction in a solvent, reaction temperature is 80 130 DEG C, and reaction gauge pressure is 1.0 5.0MPa, the reaction time for 3~for 24 hours；Catalyst is Anderson type polyacid parents or the parent that polyacid is modified；2) after oxidation reaction, Filtration of catalyst adds extractant and water, obtains organic phase and water phase；Organic phase obtains benzoic acid through drying, filtering, concentration and purification process.The Anderson types polyacid that the present invention uses reactivity high is catalyst, single-minded high selectivity, recoverable；Using hydrogen peroxide, air or oxygen as oxidant, cost can be reduced and reduce the generation of the three wastes；Reaction condition is mild, high income, easy to operate, is suitable for industrialized production.
Description
Technical field
The invention belongs to the catalytic fields of technical field of catalytic chemistry, especially polyoxometallate, and in particular to a kind of
The method that Anderson type polyacid catalysis oxidations prepare benzoic acid.
Background technology
Benzoic acid also known as benzoic acid are colourless, tasteless flat crystal.122.13 DEG C of fusing point, 249 DEG C of boiling point are relatively close
Spend 1.2659 (15/4 DEG C).It distils rapidly at 100 DEG C, its steam has very strong irritation, easily causes to cough after sucking.It is micro-
It is dissolved in water, is soluble in the organic solvents such as ethyl alcohol, ether.Benzoic acid is weak acid, stronger than aliphatic acid.Their chemical property is similar,
Can forming salt, ester, carboxylic acid halides, amide, acid anhydrides etc., be all not easy to be aoxidized.Benzoic acid and sodium benzoate can be used as latex, toothpaste, fruit
The bacteriostatic agent of sauce or other food can also make the mordant of dyeing and red ink paste used for seals.It is also used as the intermediate of pharmacy and dyestuff, is used
In producing plasticizer and fragrance etc., also as the antirust agent of steel equipment.
Benzoic acid is mainly prepared using following synthetic method in the prior art：The direct liquid phase oxidation of toluene, O-phthalic
Acid anhydrides heats decarboxylation method and benzotrichloride Hydrolyze method.It is described in detail below.
The direct liquid phase oxidation of toluene：The technique is divided into three parts：(toluene partial oxidation generates benzene first for oxidation reaction part
Acid), distillation fraction (removing unreacted toluene), rectifying part (first remove light component, after obtain benzoic acid, remaining recombination
Divide and benzyl ester tower is gone to handle).(Abdel-Rahman L H,Abu-Dief A M,Adam M S S,et al.Some New
Nano-sized Mononuclear Cu(II)Schiff Base Complexes:Design,Characterization,
Molecular Modeling and Catalytic Potentials in Benzyl Alcohol Oxidation[J]
.Catalysis Letters,2016,146(8):1-24.Tang S,Liang B,Wu P,et al.Kinetics of
liquid-phase oxidation of toluene to benzoic acid by air[J].Chemical Reaction
Engineering&Technology,2005.Yu L,Hong W,Zhang Z H,et al.Intramolecular
Sandwich Complexation of Light Lanthanoid Nitrates with Bis(benzo-12-crown-4)
s:Enhanced Selectivity for Eu[J].Journal of Inclusion Phenomena and
Macrocyclic Chemistry,1999,34(2):189-197.).This three parts is all intermittently operated, the energy used
With generate waste heat all there is wave crest, trough phenomenon, reaction heat cannot efficiently use, rectifying part high energy consumption, equipment not only it is small simultaneously
And it is more, while food pharmaceutical grade is produced using water soluble method, consumes a large amount of tap water and steam, wastewater flow rate is big and processing is tired
It is difficult.
Phthalic anhydride heats decarboxylation method：(Kumagai S,Grause G,Kameda T,et al.Improvement
of the Benzene Yield During Pyrolysis of Terephthalic Acid Using a CaO Fixed-
Bed Reactor[J].Industrial&Engineering Chemistry Research,2011,50(11).Kumagai
S,Grause G,Kameda T,et al.Decomposition of Gaseous Terephthalic Acid in the
Presence of CaO[J].Industrial&Engineering Chemistry Research,2011,50(4):1831-
1836.Masuda T,Miwa Y,Tamagawa A,et al.Degradation of waste poly(ethylene
terephthalate)in a steam atmosphere to recover terephthalic acid and to
minimize carbonaceous residue[J].Polymer Degradation&Stability,1997,58(3):
315-320.).In the method, there is the generation of side reaction in addition to main reaction, makes in product containing a small amount of biphenyl, O-phthalic
Acid, benzophenone etc..Its because in product usual objectionable impurities it is less, be current external small lot production pharmaceutical grade benzene first prevailing
The method of acid, but the preparation manipulation process of high purity product is cumbersome, it is of high cost.
Benzotrichloride Hydrolyze method：Toluene and chlorine carry out optical chlorinating reaction under the conditions of certain temperature and pressure, then again and
Water carries out benzoic acid crude product is obtained by the reaction that (Tang Shengwei, Liang Bin, Wu Pan wait the dynamics research of liquid-phase oxidation of toluene reaction process
[J] Chemical Reaction Engineerings and technique, 2005,21 (4):333-339.).This method and step is more, and by-product is more and hardly possible detaches,
It needs to consume chlorine, the environmental pollutions such as HCl/water solution of discharge are serious, and therefore, the typically just chlorination toluene hydrolysis of this method is made
The compensation process that benzaldehyde or benzyl alcohol by-product recovery utilize.
Invention content
The technical problem to be solved in the present invention is to provide a kind of utilizations at low cost, simple for process, environmentally protective
Anderson type polyacid is the method that catalyst oxidation prepares high-quality benzoic acid.The present invention avoids in the oxidation reaction stage
Use initiator, especially halogen initiator so that obtained product has high-quality, can be widely used in food,
The fields such as drug, daily use chemicals.Reaction condition of the present invention is mild simultaneously, easy to operate using one kettle way, product yield high；It urges simultaneously
Agent facilitates recycling, can reuse, be suitable for industrialized production.
The present inventor is by the study found that using toluene as raw material, in the presence of Halogen Anderson type polyacid catalyst,
It is aoxidized by oxidant (air, oxygen or hydrogen peroxide), the benzoic acid of high-quality can be obtained, reactive chemistry formula is as follows：
The present invention provides a kind of method that Anderson types polyacid catalysis oxidation prepares benzoic acid, is as follows：
1) by toluene under catalyst, oxidant and Additive, oxidation reaction occurs in a solvent, reaction temperature is
80-130 DEG C, reaction gauge pressure be 1.0-5.0MPa, the reaction time be 3~for 24 hours；The catalyst is that polyacid parent or polyacid are modified
Parent；Structural formula [the NH of polyacid parent4]3[M1Mo6O18(OH)6] or [NH4]4[M2Mo6O18(OH)6] indicate, polyacid modification
Parent structural formula [N (C4H9)4]3[M1Mo6O18(OH)3{(OCH2)3CR }] or [N (C4H9)4]4[M2Mo6O18(OH)3
{(OCH2)3CR }] it indicates；Wherein：M1For Mn, Fe or Al, M2For Cu, Co or Ni, R NH2、CH2OH、CH3Or NO2；
2) after oxidation reaction, Filtration of catalyst adds extractant and water, obtains organic phase and water phase；
Organic phase obtains benzoic acid through drying, filtering, concentration and purification process.
In the present invention, in step 1), the molar ratio of catalyst and toluene is 1:1000~1:100.
In the present invention, in step 1), the molar ratio of catalyst and toluene is 1:150~1:100.
In the present invention, in step 1), oxidant is air, oxygen or hydrogen peroxide.
In the present invention, in step 1), when oxidant is hydrogen peroxide, using 30wt% hydrogen peroxide, hydrogen peroxide and toluene
Molar ratio be 2:1~5:1.
In the present invention, in step 1), additive is any one or several in sodium acetate, sodium hydroxide or sodium carbonate；Add
It is 1 to add the molar ratio of agent and toluene:100~1:10.
In the present invention, in step 1), solvent is selected from acetic acid, dimethyl succinate, diethyl succinate or malonic acid diethyl
Any in ester, the volume mass ratio of solvent and toluene is 2:1~50:1ml/g.
In the present invention, in step 1), reaction temperature is 80-120 DEG C, and reaction gauge pressure is 1.0-4.0MPa, reaction time 5
~16h.When gauge pressure is 0, as normal pressure.
In the present invention, in step 1), reaction temperature is 80-100 DEG C, and reaction gauge pressure is 1.0-2.0MPa, reaction time 8
~12h.
In the present invention, in step 2), purified using column chromatography.
Compared to the prior art, of the invention main to have the beneficial effect that：
(1), the oxidation reaction stage selects Fe-Anderson type heteropolyacid catalysts, avoids the use of initiator, especially
It is that of avoiding the use of halogen initiator, and obtained benzoic acid product has high-quality, can be used for food, medicine, day
With fields such as chemistry；
(2), when oxidation reaction uses hydrogen peroxide as oxidant, product only has water, without other pollutants, has warp
The characteristics of Ji, environmental protection, green high-efficient；
(3), convenient catalyst recycles, and the catalyst recycled is applied mechanically repeatedly, does not find decay of activity；
(4), the present invention can greatly reduce cost, reduce the generation of the three wastes, mitigate environmental protection pressure；
(4), easy to operate, reaction condition is mild, product yield high, be suitable for industrialized production.
Description of the drawings
Fig. 1 is embodiment 1- embodiments 3 with the Anderson type polyoxometallates [NH that iron is metal center4]3
[FeMo6O18(OH)6] infrared spectrogram.
Fig. 2 is the Tris-NH using iron as metal center in embodiment 4-52The Anderson types polyacid ([N (C of modification4H9)4]3
[FeMo6O18{(OCH2)3CNH2}2]) infrared spectrogram.
Fig. 3 is the Anderson type polyoxometallates [NH that iron is metal center in embodiment 14]3[FeMo6O18(OH)6]
IR Characterization figure after recycled for multiple times.
Specific implementation mode
It is further explained and described the content of present invention below by way of specific implementation mode, but embodiment is understood not to pair
The limitation of the scope of the present invention.Fig. 1 is with iron be metal center Anderson type polyoxometallates infrared spectrogram.
Fig. 2 is the Tris-NH using iron as metal center2The infrared spectrogram of the Anderson type polyacid of modification.
Embodiment 1
By the toluene of 0.9214g (0.01mol), the Fe-Anderson type polyoxometallates of 0.01202g (1mol%)
Catalyst ([NH4]3[FeMo6O18(OH)6]), the solvent fourth of the sodium hydroxide additive of 0.0040g (0.1equiv) and 5mL
Acid dimethyl is put into dry reaction test tube, after being warming up to 80 DEG C, is reacted in air, is 1.0MPa in pressure (gauge pressure)
Lower insulation reaction for 24 hours after, stop reaction, with ethyl acetate by reaction system extract 3 times, obtained product is removed under reduced pressure molten
Agent, column chromatography for separation obtain benzoic acid, obtain product 0.9648g, yield 79%.Fig. 3 is that iron is metal center in embodiment 1
Anderson type polyoxometallates [NH4]3[FeMo6O18(OH)6] IR Characterization figure after 6 times recycle.
Embodiment 2
By the toluene of 0.9214g (0.01mol), the Fe-Anderson type polyoxometallates of 0.01202g (1mol%)
Catalyst ([NH4]3[FeMo6O18(OH)6]), the solvent acetic acids of the carbonic acid sodium additives of 0.0106 (0.1equiv) and 3mL
It puts into the hydrothermal reaction kettle of inner liner polytetrafluoroethylene, it is noted that first check whether equipment has damage using preceding, to hydro-thermal reaction
It is added solvent and raw material in kettle container, after stirring and dissolving, nitrogen is blown into container for a period of time, system is made to be in inert atmosphere
In, hydrothermal reaction kettle lid, which is tightened, in use adds catalyst and places it in baking oven, after being warming up to 120 DEG C, connects oxygen
Tank, it is 1.0MPa or so to make pressure (gauge pressure), after insulation reaction 8h, stops reaction.Wait for that autoclave body cooled to room temperature opens kettle
Lid is extracted reaction system 3 times with ethyl acetate, and solvent is removed under reduced pressure in obtained product, and column chromatography for separation obtains benzoic acid,
Obtain product 1.1601g, yield 95%.
Embodiment 3
By the toluene of 0.9214g (0.01mol), the Fe-Anderson type polyoxometallates of 0.01202g (1mol%)
Catalyst ([NH4]3[FeMo6O18(OH)6]), the carbonic acid sodium additives of 0.0106g (0.1equiv), 30% mistake of 0.03mol
The solvent acetic acid of hydrogen oxide and 8mL are put into dry and clean pressure pipe, after being warming up to 110 DEG C, in pressure (table
Pressure) it is to stop reaction under 1.0MPa after insulation reaction 12h, reaction system is extracted 3 times with ethyl acetate, obtained product
Solvent is removed under reduced pressure, column chromatography for separation obtains benzoic acid, obtains product 0.9769g, yield 80%.
Embodiment 4
By the toluene of 0.9214g (0.01mol), the Fe- of the Tris Derivatives Modifieds of 0.01883g (1mol%)
Anderson types polyacid ([N (C4H9)4]3[FeMo6O18{(OCH2)3CNH2}2]), the addition of the sodium carbonate of 0.0106g (0.1equiv)
Agent, the hydrogen peroxide of 30wt% and the solvent acetic acid of 30mL of the hydrogen peroxide containing 0.03mol put into dry and totally resistance to
In pressure pipe, after being warming up to 100 DEG C, in the case where pressure (gauge pressure) is 1.0MPa after insulation reaction 10h, stops reaction, use ethyl acetate
Reaction system is extracted 3 times, solvent is removed under reduced pressure in obtained product, and column chromatography for separation obtains benzoic acid, obtains product
1.0746g yield 88%.
Embodiment 5
By the toluene of 0.9214g (0.01mol), the Fe- of the Tris Derivatives Modifieds of 0.01883g (1mol%)
Anderson types polyacid ([N (C4H9)4]3[FeMo6O18{(OCH2)3CNH2}2]), the addition of the sodium carbonate of 0.0106g (0.1equiv)
Agent, the hydrogen peroxide of the 30wt% of the hydrogen peroxide containing 0.03mol and the solvent diethyl succinate of 30mL put into it is dry and
In clean pressure pipe, after being warming up to 80 DEG C, in the case where pressure (gauge pressure) is 1.0MPa after insulation reaction 12h, stops reaction, use second
Acetoacetic ester extracts reaction system 3 times, and solvent is removed under reduced pressure in obtained product, and column chromatography for separation obtains benzoic acid, is produced
Product 1.1845g, yield 97%.
The specific data of nucleus magnetic hydrogen spectrum figure for the benzoic acid that embodiment 1-5 is obtained are as follows：
1H NMR (501MHz, DMSO) δ 12.97 (s, 1H), 7.96 (d, J=7.2Hz, 2H), 7.62 (t, J=7.4Hz,
1H), 7.50 (t, J=7.7Hz, 2H)
The specific data of carbon spectrogram for the benzoic acid that embodiment 1-5 is obtained are as follows：
13C NMR(126MHz,DMSO)δ167.79(s),133.30(s),131.24(s),129.73(s),129.01
(s).
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But it is every without departing from technical solution of the present invention content, according to the technical essence of the invention to above example institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention, used herein is each
A bibliography, which is hereby incorporated by reference.
Claims (10)
1. a kind of method that Anderson types polyacid catalysis oxidation prepares benzoic acid, which is characterized in that be as follows：
1) by toluene under catalyst, oxidant and Additive, oxidation reaction, reaction temperature 80- occur in a solvent
130 DEG C, reaction gauge pressure be 1.0-5.0MPa, the reaction time be 3~for 24 hours；The catalyst is that polyacid parent or polyacid are modified
Parent；Structural formula [the NH of polyacid parent4]3[M1Mo6O18(OH)6] or [NH4]4[M2Mo6O18(OH)6] indicate, polyacid modification
Structural formula [N (the C of parent4H9)4]3[M1Mo6O18(OH)3{(OCH2)3CR }] or [N (C4H9)4]4[M2Mo6O18(OH)3
{(OCH2)3CR }] it indicates；Wherein：M1For Mn, Fe or Al, M2For Cu, Co or Ni, R NH2、CH2OH、CH3Or NO2；
2) after oxidation reaction, Filtration of catalyst adds extractant and water, obtains organic phase and water phase；It is organic
Mutually benzoic acid is obtained through drying, filtering, concentration and purification process.
2. according to the method described in claim 1, it is characterized in that, in step 1), the molar ratio of catalyst and toluene is 1:
1000~1:100.
3. according to the method described in claim 1, it is characterized in that, in step 1), the molar ratio of catalyst and toluene is 1:150
~1:100.
4. according to the method described in claim 1, it is characterized in that, in step 1), oxidant is air, oxygen or peroxidating
Hydrogen.
5. according to the method described in claim 4, it is characterized in that, in step 1), when oxidant is hydrogen peroxide, use
The molar ratio of 30wt% hydrogen peroxide, hydrogen peroxide and toluene is 2:1~5:1.
6. according to the method described in claim 1, it is characterized in that, in step 1), additive be selected from sodium acetate, sodium hydroxide or
It is any one or several in sodium carbonate；The molar ratio of additive and toluene is 1:100~1:10.
7. according to the method described in claim 1, it is characterized in that, in step 1), solvent be selected from acetic acid, dimethyl succinate,
Any in diethyl succinate or diethyl malonate, the volume mass ratio of solvent and toluene is 2:1~50:1ml/g.
8. according to the method described in claim 1, it is characterized in that, in step 1), reaction temperature is 80-120 DEG C, reacts gauge pressure
For 1.0-4.0MPa, the reaction time is 5~16h.
9. the method according to claim 1 or 8, which is characterized in that in step 1), reaction temperature is 80-100 DEG C, reaction
Gauge pressure is 1.0-2.0MPa, and the reaction time is 8~12h.
10. according to the method described in claim 1, it is characterized in that, in step 2), purified using column chromatography.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613269A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of method of preparing phenylformic acid through liquid phase oxidation of methylbenzene |
| CN107698436A (en) * | 2016-08-09 | 2018-02-16 | 朱翠英 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
-
2018
- 2018-03-08 CN CN201810191830.5A patent/CN108383710A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613269A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of method of preparing phenylformic acid through liquid phase oxidation of methylbenzene |
| CN107698436A (en) * | 2016-08-09 | 2018-02-16 | 朱翠英 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
Non-Patent Citations (1)
| Title |
|---|
| HAN YU等: "An Efficient Iron(III)-Catalyzed Aerobic Oxidation of Aldehydes in Water for the Green Preparation of Carboxylic Acids", 《ANGEW. CHEM. INT. ED.》 * |
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Application publication date: 20180810 |