CN114773170A - Preparation process of m-phthalaldehyde - Google Patents
Preparation process of m-phthalaldehyde Download PDFInfo
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- CN114773170A CN114773170A CN202210479207.6A CN202210479207A CN114773170A CN 114773170 A CN114773170 A CN 114773170A CN 202210479207 A CN202210479207 A CN 202210479207A CN 114773170 A CN114773170 A CN 114773170A
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- IZALUMVGBVKPJD-UHFFFAOYSA-N benzene-1,3-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=C1 IZALUMVGBVKPJD-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims abstract description 74
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 26
- 239000012074 organic phase Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 239000005457 ice water Substances 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 60
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000012847 fine chemical Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 206010039073 rheumatoid arthritis Diseases 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- -1 N- (naphthalene-1-yl) hydrazine methionine amide Chemical compound 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 229910018162 SeO2 Inorganic materials 0.000 description 1
- 108700005077 Viral Genes Proteins 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 description 1
- 229960000789 guanidine hydrochloride Drugs 0.000 description 1
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229960003350 isoniazid Drugs 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- KFUSANSHCADHNJ-UHFFFAOYSA-N pyridine-3-carbohydrazide Chemical compound NNC(=O)C1=CC=CN=C1 KFUSANSHCADHNJ-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation process of m-phthalaldehyde, which uses MnO2Is used as oxidant, and m-xylene is oxidized in acid environment to obtain m-phthalaldehyde. The invention relates to a preparation process of m-phthalaldehyde, wherein the raw material still adopts cheaper m-xylene and MnO as2Is used as an oxidant, m-xylene is directly oxidized in an acid environment to obtain m-phthalaldehyde, the production cost is saved, the oxidation yield is high, and the method is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of fine chemical synthesis, in particular to a preparation process of m-phthalaldehyde.
Background
Isophthalaldehyde (IPAL) is a very important fine chemical intermediate and is widely applied to the industries of medicines, dyes and the like. For example, a novel Polyethyleneimine (PEI) derivative IPEI constructed with IPAL as a linker can be used as a non-viral gene vector for the treatment of Rheumatoid Arthritis (RA); IPAL can also react with isoniazid, nicotinic acid hydrazide and 2-pyridine formylhydrazine respectively to synthesize a Schiff base ligand containing a pyridine ring, and the ligand compound can form metal gel with copper acetate in different solvents through coordination action, and is a novel supermolecule work with great development potentialAn energy material; in addition, a simple and efficient fluorescent probe is synthesized by IPAL and N- (naphthalene-1-yl) hydrazine methionine amide, and Fe in organisms and the environment can be efficiently detected3+And (4) content. The m-phthalaldehyde has good market prospect, so higher requirements are put forward for the preparation process of the m-phthalaldehyde.
At present, in the industrial synthesis process of m-phthalaldehyde, m-xylene is mainly used as a raw material, a polychlorinated benzyl mixture is obtained through chlorination reaction, and m-phthalaldehyde is obtained through catalytic oxidation, wherein the synthesis route is as follows:
in the prior art, nitric acid is used as a catalyst in the oxidation reaction, so that the protection requirement is high, the operation is inconvenient, and the corrosion to a production device is serious. Yangming et al (literature: improvement of high-purity m-phthalaldehyde synthesis process, fine chemical intermediate 2007, 37 (4): 32-33, 52) and Zhousheng et al (patent: CN106431863A) adopt expensive urotropine (HMTA) as an oxidant, thereby solving the pollution problem of nitric acid. However, the chlorine used in the process is taken as a toxic gas with strong pungent smell, the production safety is still low, the chlorination depth is difficult to control, the product quality is low, multiple refining is needed, and the cost is high.
In consideration of the problem of large pollution of a chloro-oxidation process, Yangming and the like (the document: synthesis of m-phthalaldehyde, fine chemical industry, 2014, 31 (4): 532-533) and U.S. Pat. No. 4,4845305) disclose a method for preparing m-phthalaldehyde by using m-xylylenediamine as a raw material and urotropine as an oxidant, wherein the synthesis route is as follows:
the method has a simple flow, but the m-xylylenediamine is expensive as a raw material, and a byproduct, namely, the guanidine hydrochloride, is generated in the reaction, so that the raw material is wasted, and the environment is seriously polluted when the m-xylylenediamine is discharged out of a system. The overall yield is not high, and the process has certain defects.
Thus, Chenbenshu et al (patent: CN106565438A) proposed direct oxidation of m-xylene, still starting from m-xylene, to isophthalaldehyde, the synthetic route is as follows:
however, the first method (left-side reaction type) uses manganese acetate (or cobalt acetate, iron acetate) as a catalyst, and since it is distributed in the reaction solution, the catalyst is carried when the generated acetic acid flows out of the reactor, thereby reducing the concentration of manganese acetate in the reaction solution, shortening the life of the catalyst, accelerating the replacement frequency, increasing the consumption, and being not suitable for long-term mass production. The second method (right-side reaction formula) uses hydrogen peroxide as an oxidant, and the reaction temperature is 85-90 ℃, but at this temperature, hydrogen peroxide is very easy to decompose, resulting in a decrease in the yield of the reaction.
Disclosure of Invention
In order to solve the various defects in the method for synthesizing the m-phthalaldehyde by directly oxidizing the m-xylene, the invention discloses an improved m-phthalaldehyde preparation process, wherein the raw material still adopts the cheap m-xylene and MnO2Is used as an oxidant, m-xylene is directly oxidized in an acid environment to obtain m-phthalaldehyde, the production cost is saved, the oxidation yield is high, and the method is suitable for industrial production.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation process of m-phthalaldehyde, which is prepared from MnO2Is used as oxidant, and m-xylene is oxidized in acid environment to obtain m-phthalaldehyde.
In some embodiments, the acidic environment is created by the addition of H2SO4And (4) obtaining.
In some embodiments, the H is2SO4Is H with the mass concentration of 65-70 percent2SO4. The synthesis route is as follows:
in some embodiments, m-xylene is reacted with H2SO4The mass-to-volume ratio of (A) to (B) is 1: 5-7. I.e. the mass unit of m-xylene is g, H2SO4The volume unit of (a) is mL.
In some embodiments, m-xylene is reacted with H2SO4The mass-to-volume ratio of (2) is 1: 6. I.e. the mass unit of m-xylene is g, H2SO4The volume unit of (a) is mL.
In some embodiments, the oxidation reaction is carried out at room temperature.
In some embodiments, meta-xylene is combined with MnO2The molar ratio of (A) to (B) is 1: 4-7.
In some embodiments, meta-xylene is combined with MnO2The molar ratio of (A) to (B) is 1: 5.5-6.5.
In some embodiments, meta-xylene is combined with MnO2In a molar ratio of 1: 6.
In some embodiments, specifically: adding m-xylene and MnO2And H2SO4Stirring and reacting for 20-24 h at room temperature; and then adding the reaction solution into an ice-water mixture, stirring, filtering, extracting, combining organic phases, washing, drying and concentrating to obtain the m-phthalaldehyde.
In some embodiments, in particular: adding m-xylene and MnO2And H2SO4Stirring and reacting for 20-24 h at room temperature; and then adding the reaction solution into the ice water mixture, stirring, filtering, extracting, combining organic phases, washing, drying and concentrating to obtain the isophthalaldehyde.
Further, the extraction employed Dichloromethane (DCM) as the extract.
Further, the washing is to wash the combined organic phases with an aqueous sodium bicarbonate solution, water and saturated sodium chloride in sequence.
Further, the drying is performed using anhydrous sodium sulfate.
In some embodiments, TLC is used to follow the progress of the reaction; the developing solvent for TLC is selected from petroleum ether and ethyl acetate. Further, the volume ratio of the petroleum ether to the ethyl acetate in the developing solvent is 3: 1.
Compared with the prior art of the synthesis method of isophthalaldehyde, the invention has the following advantages and beneficial effects:
the m-xylene is still selected as the initial raw material in the m-phthalaldehyde preparation process provided by the invention, so that expensive m-xylylenediamine is avoided. After the cost of raw materials is controlled, a direct oxidation method is adopted. For oxidation of the aromatic side chain methyl group to an aldehyde group, SeO2If the compound is used as an oxidizing agent, the compound has considerable toxicity, high price and mild conditions; CrO3If the compound is used as an oxidizing agent, the yield is low and the post-treatment is difficult. By comprehensive comparison, MnO is selected2(acidic conditions) as oxidizing agent, considering HCl and HNO3Will be in contact with MnO2The reaction produces chlorine (harmful to human health) and nitric oxide (the first-class atmospheric pollutants that cause photochemical smog), thus utilizing H2SO4Creating acidic conditions (with MnO)2The reaction producing only O2) And can oxidize the m-xylene at room temperature, and has mild conditions, safety and environmental protection. The post-treatment only needs to filter out MnO2That is, the method is directed to m-xylene and MnO2And H2SO4Addition amount ratio of (1) and (H)2SO4The mass concentration is optimized, and the reaction yield is improved. In conclusion, the process saves the production cost, has high oxidation yield, mild reaction conditions and simple post-treatment, is safe and environment-friendly, and is more suitable for industrial production.
The conception, specific structure and technical effects of the present invention will be further described in conjunction with the embodiments below, so that the objects, features and effects of the present invention can be fully understood.
Detailed Description
In order to make the technical means, the inventive features, the objectives and the effects of the invention easy to understand, the invention will be further described with reference to the following embodiments. However, the present invention is not limited to the following embodiments.
Example 1
To a 250mL flask was added 100mL 70% H2SO420.0g m-xylene (0.19mol) and 98.2g MnO2(1.13mol), stirring at room temperature for 20-24 h, and tracking the reaction by TLC. And (3) after the reaction is finished, adding the reaction solution into an ice-water mixture, stirring and filtering. The reaction was then extracted 3 times with Dichloromethane (DCM) and the organic phases combined. The combined organic phases were washed with aqueous sodium bicarbonate, water and saturated sodium chloride in that order for 1 time, dried over anhydrous sodium sulfate and concentrated to give the product isophthalaldehyde 22.0g (0.164mol) in 86.4% yield.
Comparative example 1
To a 250mL flask was added 100mL 70% H2SO420.0g of m-xylene (0.19mol) and 65.2g of MnO2(0.75mol), stirring at room temperature for 20-24 h, and tracking the reaction by TLC. And after the reaction is finished, adding the reaction solution into an ice-water mixture, stirring and filtering. The reaction was then extracted 3 times with Dichloromethane (DCM) and the organic phases combined. The combined organic phases were washed with aqueous sodium bicarbonate, water and saturated sodium chloride in that order for 1 time, dried over anhydrous sodium sulfate and concentrated to give the product isophthalaldehyde 18.7g (0.139mol) with a yield of 73.2%.
Comparative example 2
To a 250mL flask was added 100mL 70% H2SO420.0g m-xylene (0.19mol) and 81.7g MnO2(0.94mol), stirring at room temperature for 20-24 h, and tracking the reaction by TLC. And after the reaction is finished, adding the reaction solution into an ice-water mixture, stirring and filtering. The reaction was then extracted 3 times with Dichloromethane (DCM) and the organic phases combined. The combined organic phases were washed with aqueous sodium bicarbonate, water and saturated sodium chloride in that order for 1 time, dried over anhydrous sodium sulfate and concentrated to give 20.3g (0.151mol) of isophthalaldehyde, yield 79.7%.
Comparative example 3
To a 250mL flask was added 100mL 70% H2SO420.0g of m-xylene (0.19mol) and 114.4g of MnO2(1.32mol), stirring at room temperature for 20-24 h, and tracking the reaction by TLC. And after the reaction is finished, adding the reaction solution into an ice-water mixture, stirring and filtering. The reaction was then extracted 3 times with Dichloromethane (DCM), and the organic layers were combinedAnd (4) organic phase. The combined organic phases were then washed with aqueous sodium bicarbonate, water and saturated sodium chloride in that order for 1 time, dried over anhydrous sodium sulfate and concentrated to give the product isophthalaldehyde 20.7g (0.154mol) with a yield of 81.3%.
Example 2
To a 250mL flask was added 120mL 70% H2SO420.0g m-xylene (0.19mol) and 98.2g MnO2(1.13mol), stirring at room temperature for 20-24 h, and tracking the reaction by TLC. And after the reaction is finished, adding the reaction solution into an ice-water mixture, stirring and filtering. The reaction was then extracted 3 times with Dichloromethane (DCM) and the organic phases combined. The combined organic phases were then washed with aqueous sodium bicarbonate, water and saturated sodium chloride 1 time each in sequence, dried over anhydrous sodium sulfate and concentrated to give the product isophthalaldehyde 23.7g (0.177mol) with a yield of 93.1%.
Comparative example 4
Into a 250mL flask was added 140mL of 70% H2SO420.0g of m-xylene (0.19mol) and 98.2g of MnO2(1.13mol), stirring at room temperature for 20-24 h, and tracking the reaction by TLC. And after the reaction is finished, adding the reaction solution into an ice-water mixture, stirring and filtering. The reaction was then extracted 3 times with Dichloromethane (DCM) and the organic phases combined. The combined organic phases were washed with aqueous sodium bicarbonate, water and saturated sodium chloride in that order for 1 time, dried over anhydrous sodium sulfate and concentrated to give the product isophthalaldehyde 22.6g (0.168mol) with a yield of 88.6%.
Example 3
To a 250mL flask was added 120mL of 65% H2SO420.0g of m-xylene (0.19mol) and 98.2g of MnO2(1.13mol), stirring at room temperature for 20-24 h, and tracking the reaction by TLC. And after the reaction is finished, adding the reaction solution into an ice-water mixture, stirring and filtering. The reaction was then extracted 3 times with Dichloromethane (DCM) and the organic phases combined. The combined organic phases were washed with aqueous sodium bicarbonate, water and saturated sodium chloride in that order for 1 time, dried over anhydrous sodium sulfate and concentrated to give the product isophthalaldehyde 23.7g (0.176mol) in 92.8% yield.
Comparative example 5
Into a 250mL flask was added 120mL of 60% H2SO420.0g m-xylene (0.19mol) and 98.2g MnO2(1.13mol), stirring at room temperature for 20-24 h, and tracking the reaction by TLC. And (3) after the reaction is finished, adding the reaction solution into an ice-water mixture, stirring and filtering. The reaction was then extracted 3 times with Dichloromethane (DCM) and the organic phases combined. The combined organic phases were washed with aqueous sodium bicarbonate, water and saturated sodium chloride in that order for 1 time, dried over anhydrous sodium sulfate and concentrated to give the product isophthalaldehyde 22.2g (0.166mol) in 87.3% yield.
Comparative example 6
To a 250mL flask was added 120mL of 75% H2SO420.0g of m-xylene (0.19mol) and 98.2g of MnO2(1.13mol), stirring at room temperature for 20-24 h, and tracking the reaction by TLC. And after the reaction is finished, adding the reaction solution into an ice-water mixture, stirring and filtering. The reaction was then extracted 3 times with Dichloromethane (DCM) and the organic phases combined. The combined organic phases were then washed with aqueous sodium bicarbonate, water and saturated sodium chloride in that order for 1 time, dried over anhydrous sodium sulfate and concentrated to give the product isophthalaldehyde 23.0g (0.171mol) with a yield of 90.4%.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (10)
1. A process for preparing m-phthalaldehyde, which is characterized in that MnO is used2As an oxidant, m-xylene is oxidized in an acidic environment to obtain m-phthalaldehyde.
2. A process for preparing isophthalaldehyde according to claim 1, wherein the acidic environment is maintained by the addition of H2SO4And (4) obtaining.
3. The process for preparing isophthalaldehyde according to claim 2, wherein the H is2SO4Is H with the mass concentration of 65-70 percent2SO4。
4. A process for preparing isophthalaldehyde as claimed in claim 2, wherein m-xylene and H are reacted2SO4The mass-to-volume ratio of (A) to (B) is 1: 5-7.
5. A process for preparing isophthalaldehyde according to claim 1, wherein the oxidation reaction is carried out at room temperature.
6. A process for the preparation of isophthalaldehyde as claimed in claim 1, wherein metaxylene is in contact with MnO2The molar ratio of (A) to (B) is 1: 4-7.
7. A process for preparing isophthalaldehyde according to claim 6, wherein m-xylene and MnO are present2In a molar ratio of 1: 6.
8. A process for preparing isophthalaldehyde according to claim 1, which comprises: adding m-xylene and MnO2And H2SO4Stirring and reacting for 20-24 h at room temperature; and then adding the reaction solution into an ice-water mixture, stirring, filtering, extracting, combining organic phases, washing, drying and concentrating to obtain the m-phthalaldehyde.
9. A process for preparing isophthalaldehyde according to claim 8, which comprises: adding m-xylene and MnO2And H2SO4Stirring and reacting for 20-24 h at room temperature; and then adding the reaction solution into an ice-water mixture, stirring, filtering, extracting, combining organic phases, washing, drying and concentrating to obtain the m-phthalaldehyde.
10. A process for preparing isophthalaldehyde according to claim 1, wherein the progress of the reaction is followed by TLC; the developing solvent of the TLC is selected from petroleum ether and ethyl acetate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628861A (en) * | 2009-06-22 | 2010-01-20 | 徐州华日化学工业有限公司 | Method for synthesizing 2, 5-dichloro-phthaldialdehyde |
| CN106565438A (en) * | 2015-10-10 | 2017-04-19 | 南京欧信医药技术有限公司 | Preparation method of isophthalaldehyde |
| CN107032969A (en) * | 2017-05-25 | 2017-08-11 | 钦州学院 | The technique that a kind of liquid-phase oxidation of toluene prepares benzaldehyde |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628861A (en) * | 2009-06-22 | 2010-01-20 | 徐州华日化学工业有限公司 | Method for synthesizing 2, 5-dichloro-phthaldialdehyde |
| CN106565438A (en) * | 2015-10-10 | 2017-04-19 | 南京欧信医药技术有限公司 | Preparation method of isophthalaldehyde |
| CN107032969A (en) * | 2017-05-25 | 2017-08-11 | 钦州学院 | The technique that a kind of liquid-phase oxidation of toluene prepares benzaldehyde |
Non-Patent Citations (1)
| Title |
|---|
| 李国防;胡春华;赵文献;郭保国;: "甲苯制备苯甲醛合成工艺的改进", 化学试剂, no. 06, pages 561 - 564 * |
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