CN114907196B - Method for preparing carbonyl compound by aryl substituted o-diol oxidative cleavage - Google Patents
Method for preparing carbonyl compound by aryl substituted o-diol oxidative cleavage Download PDFInfo
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- 238000007248 oxidative elimination reaction Methods 0.000 title claims abstract description 23
- 150000001728 carbonyl compounds Chemical class 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 25
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- -1 benzoic acid compound Chemical class 0.000 claims description 15
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 10
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 10
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 10
- 239000005711 Benzoic acid Substances 0.000 claims description 9
- 235000010233 benzoic acid Nutrition 0.000 claims description 9
- 239000012965 benzophenone Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 2
- 238000005336 cracking Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 6
- 150000002009 diols Chemical group 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- GWVWUZJOQHWMFB-UHFFFAOYSA-N 1,1,2-triphenylethane-1,2-diol Chemical compound C=1C=CC=CC=1C(O)(C=1C=CC=CC=1)C(O)C1=CC=CC=C1 GWVWUZJOQHWMFB-UHFFFAOYSA-N 0.000 description 1
- YOCSNHRJFCUGEU-UHFFFAOYSA-N 1,2-bis(4-methylphenyl)-1,2-diphenylethane-1,2-diol Chemical compound C1=CC(C)=CC=C1C(O)(C(O)(C=1C=CC=CC=1)C=1C=CC(C)=CC=1)C1=CC=CC=C1 YOCSNHRJFCUGEU-UHFFFAOYSA-N 0.000 description 1
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 1
- BBYDXOIZLAWGSL-UHFFFAOYSA-N 4-fluorobenzoic acid Chemical compound OC(=O)C1=CC=C(F)C=C1 BBYDXOIZLAWGSL-UHFFFAOYSA-N 0.000 description 1
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 1
- PNZVFASWDSMJER-UHFFFAOYSA-N acetic acid;lead Chemical group [Pb].CC(O)=O PNZVFASWDSMJER-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Chemical group CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- IHPDTPWNFBQHEB-UHFFFAOYSA-N hydrobenzoin Chemical compound C=1C=CC=CC=1C(O)C(O)C1=CC=CC=C1 IHPDTPWNFBQHEB-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical group IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012286 potassium permanganate Chemical group 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
-
- 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
- C07C51/305—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with sulfur or sulfur-containing compounds
-
- 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
Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing a carbonyl compound through aryl-substituted o-diol oxidative cleavage. The reaction equation is shown as a formula (1), and the reaction process is as follows: dispersing the aryl substituted o-diol compound, persulfate and sulfate in a solvent, and heating and refluxing until the reaction is complete to obtain an oxidative cracking product;wherein R is 1 、R 2 、R 3 And R is 4 Independently are represented by phenyl, substituted phenyl or H, and R 1 、R 2 、R 3 And R is 4 At least one of which represents phenyl or substituted phenyl. Compared with the prior art, the technical scheme provided by the invention has the following advantages: the reagent used in the oxidation system has low cost and small safety risk of transportation and storage; the reaction solvent can be recycled; the reaction can be carried out in an aqueous organic solvent, the reaction condition is mild, and the safety is high; the by-product of the reaction is inorganic bisulfate or sulfate, which is convenient for purification and wastewater treatment.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing a carbonyl compound through aryl-substituted o-diol oxidative cleavage.
Background
Oxidative cleavage of the vicinal diol carbon-carbon bond is an important class of chemical reactions for the synthesis of carbonyl compounds. It is therefore frequently used in the synthesis of pharmaceuticals, pesticides, natural products.
Since 1928 Malaprade found that sodium periodate or periodic acid can promote oxidative cleavage of carbon-carbon bond of vicinal diols, lead tetraacetate, manganese dioxide, chromium trioxide, potassium permanganate, iodobenzene and the like were used in this oxidation reaction in succession, but most of the oxidizing agents had a certain toxicity, stability was also poor, adverse factors existed in terms of cost, preservation, transportation and solubility, and the amount of use was large, and a large amount of by-products which were not friendly to environment were produced.
In order to avoid the above problems, a "catalytic oxidation" method is widely studied, but such a method is carried out with a transition metal or a complex thereof as a catalyst and hydrogen peroxide or oxygen as an oxidizing agent. Wherein the catalyst is difficult to prepare, can not be recycled and has high toxicity of transition metal; the adopted oxidant is inflammable and explosive and needs to be carried out under more severe reaction conditions, so that the method is not suitable for industrial production.
Therefore, the development of a catalytic oxidation method which is environment-friendly, mild in condition, economical and efficient has very important significance in research on the oxidative cleavage reaction of the carbon-carbon bond of the o-diol.
Chinese patent CN102933538A provides a method for preparing carboxylic acids by oxidative cleavage of vicinal diols, in particular by reaction with sodium hypochlorite in the absence of organic solvents and without addition of catalyst at room temperature. Firstly, sodium hypochlorite is strong in corrosiveness and is not very green and environment-friendly; in addition, because of no solvent, the method can only be used for the oxidative cleavage reaction of the aliphatic o-diol compound which is liquid per se, and is not suitable for aryl substituted o-diol compound
Chinese patent CN107245029a provides a method for producing ketone compounds from o-diol compounds, which uses 1-chloromethyl-4-fluoro-1, 4-diazabicyclo [2.2.2] octane bis (tetrafluoroboric acid) salt as an oxidant, and is prepared by stirring at 70-90 ℃, extracting, drying, filtering and distilling under reduced pressure. Firstly, the adopted oxidant is not a conventional oxidant, is generally used for monofluorination reaction, is toxic, belongs to organic matters, and is large in dosage and not beneficial to recovery and treatment; in addition, it is only suitable for tetra-substituted o-diol compounds, and only ketone compounds can be prepared.
Disclosure of Invention
The invention provides a method for preparing carbonyl compounds by oxidative cleavage of aryl-substituted o-diol, which is used for solving the problems that the existing oxidative cleavage reaction conditions are not suitable for large-scale production and the like.
In order to solve the technical problems, the technical scheme of the invention is as follows: the reaction equation of the method for preparing the carbonyl compound by aryl substituted o-diol oxidative cleavage is shown as a formula (1), and the reaction process is as follows: dispersing the aryl substituted o-diol compound, persulfate and sulfate in a solvent, and heating and refluxing until the reaction is complete to obtain an oxidative cracking product;
wherein R is 1 、R 2 、R 3 And R is 4 Independently are represented by phenyl, substituted phenyl or H, and R 1 、R 2 、 R 3 And R is 4 At least one of which represents phenyl or substituted phenyl.
When R is 1 And R is 4 Wherein one is H, the product is a benzoic acid compound, or else is a benzophenone compound, similarly, when R 2 And R is 3 The product is benzoic acid compound as soon as H, otherwise benzophenone compound. Therefore, the technical scheme provided by the invention can prepare the benzoic acid and/or benzophenone compounds through the ortho-diol compounds substituted by 1,2, 3 or 4 aryl groups.
Alternatively, the substituted phenyl refers to phenyl substituted with 1 to 5 groups on phenyl, wherein the substituent on phenyl is alkyl, alkoxy or halogen.
Alternatively, the substituent is methyl, ethyl, methoxy, ethoxy, fluoro, chloro or bromo.
Optionally, the aryl substituted o-glycol compound is tetraphenyl glycol, 1, 2-diphenyl-1, 2-di-p-tolyl glycol, 1, 2-diphenyl-1, 2-di-p-chlorophenyl glycol, triphenyl glycol, diphenyl glycol, 1, 2-difluorophenyl glycol, 1, 2-p-methoxyphenyl glycol or phenyl glycol.
Alternatively, when R 1 And R is 2 When H is the same, R 3 And R is 4 The same; when R is 1 、R 2 、R 3 And R is 4 R when both are phenyl or substituted phenyl 1 And R is 2 Identical and R is 3 And R is 4 The same applies.
The symmetrical structure can be oxidized and cracked to obtain single benzoic acid compound or diphenyl ketone compound.
Optionally, the persulfate is sodium persulfate, potassium persulfate or ammonium persulfate, and the sulfate is copper sulfate pentahydrate or ferrous sulfate.
Optionally, the molar ratio of the aryl substituted o-diol compound to the persulfate is 1 (1.0-5.0).
Optionally, the molar ratio of the aryl substituted o-diol compound to the sulfate is 1 (0.01-1.0).
Optionally, the solvent is a mixed solvent of acetonitrile and water.
Optionally, the volume ratio of acetonitrile to water in the mixed solvent is 1 (0.1-10).
Optionally, the mass volume ratio of the aryl substituted o-diol compound to the solvent is 1 (5-20).
Compared with the prior art, the technical scheme provided by the invention has the following advantages:
1) The reagent used in the oxidation system has low cost and small safety risk of transportation and storage;
2) The reaction solvent can be recycled;
3) The reaction can be carried out in an aqueous organic solvent, the reaction condition is mild, and the safety is high;
4) The by-product of the reaction is inorganic bisulfate or sulfate, which is convenient for purification and wastewater treatment.
The vicinal diols are commercially available or can be prepared by oxidation of the corresponding olefins or reduction of the corresponding ketone compounds, providing a new synthetic concept for the preparation of carbonyl compounds which are otherwise difficult to prepare.
Detailed Description
For ease of understanding, the process for preparing carbonyl compounds by oxidative cleavage of the peraryl-substituted vicinal diols is described below in connection with the examples, which are to be understood as merely illustrative of the present invention and are not intended to limit the scope of the invention.
The starting materials, reagents or equipment for the reactions used in the examples were commercially available unless otherwise specified.
EXAMPLE 1 tetra-substituted O-diols
10g of tetraphenyl glycol was added to 100ml of acetonitrile and 100ml of water, 13.0g of sodium persulfate, 0.68g of copper sulfate pentahydrate was added, and the reaction was heated under reflux for 2 hours until the TLC reaction was complete. After working up, extraction with methylene chloride, concentration and purification gave 9.5g of benzophenone as a product in a yield of about 95%.
EXAMPLE 2 tetra-substituted O-diols
10g of 1, 2-diphenyl-1, 2-di-p-tolylethylene glycol was added to 100ml of acetonitrile and 100ml of water, 12.0g of sodium persulfate, 0.63g of copper sulfate pentahydrate was added, and the reaction was heated under reflux for 5 hours until the TLC reaction was complete. After working up, extraction with methylene chloride, concentration and purification give 8.5g of p-methylbenzophenone as the product in a yield of about 85%. Wherein diphenyl ethylene dione is obtained by reacting with a formative reagent of p-bromotoluene.
EXAMPLE 3 tetra-substituted O-diols
10g of 1, 2-diphenyl-1, 2-di-p-chlorophenyl ethylene glycol was added to 100ml of acetonitrile and 100ml of water, 16.4g of sodium persulfate, 0.6g of copper sulfate pentahydrate were added, and the reaction was heated under reflux for 10 hours until the TLC reaction was complete. After working up, extraction with methylene chloride, concentration and purification give 8.5g of the product 4-chlorobenzophenone with a yield of about 85%.
EXAMPLE 4 trisubstituted o-diols
10g of triphenylethylene glycol was added to 100ml of acetonitrile and 100ml of water, 32.8g of sodium persulfate, 0.8eq of copper sulfate pentahydrate was added, and the reaction was heated under reflux for 10 hours until the TLC reaction was complete. After the post-treatment, the system is extracted by methylene dichloride, and concentrated to obtain products of benzoic acid and benzophenone, 5.2g of benzophenone is obtained after separation and purification by silica gel column chromatography, and the yield is about 83%, 3.2g of benzoic acid is obtained, and the yield is about 76%.
EXAMPLE 5 disubstituted o-diols
10g of diphenylethylene glycol was added to 100ml of acetonitrile and 150ml of water, 44.4g of sodium persulfate, 1.1g of copper sulfate pentahydrate were added, and the reaction was heated under reflux for more than 12 hours until the TLC reaction was complete. The system was extracted with dichloromethane and concentrated to give 9.1g of benzoic acid as a product in 80% yield.
EXAMPLE 6 disubstituted o-diols
10g of 1, 2-difluorophenyl ethylene glycol was added to 200ml of acetonitrile and 100ml of water, sodium persulfate 38 g and copper sulfate pentahydrate 0.8g were added, and the reaction was heated under reflux for more than 8 hours until TLC was complete. The system is added into water, the precipitated solid is crude product p-fluorobenzoic acid, 9.2g is obtained after filtration and drying, and the yield is 82%.
EXAMPLE 7 disubstituted vicinal diols
10g of 1, 2-p-methoxyphenyl glycol is added into 120ml of acetonitrile and 120ml of water, 43.4g of sodium persulfate and 0.9g of copper sulfate pentahydrate are added, and the reaction is heated and refluxed for more than 12 hours until the TLC reaction is complete. The system is added into water, the precipitated solid is the crude product p-methoxybenzoic acid, 8.1g is obtained after filtration and drying, and the yield is 73%.
EXAMPLE 8 monosubstituted o-diols
10g of phenyl glycol is added into 100ml of acetonitrile and 100ml of water, 60.3g of sodium persulfate and 1.5g of copper sulfate pentahydrate are added, and the reaction is heated and refluxed for more than 15 hours until the TLC reaction is complete. The system was extracted with ethyl acetate and concentrated to give 6.6g of benzoic acid as a product in 75% yield.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting. Although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments may be modified or some or all of the technical features may be replaced with other technical features, which do not depart from the scope of the technical scheme of the embodiments of the present invention.
Claims (9)
1. A method for preparing carbonyl compounds by oxidative cleavage of aryl-substituted o-diols, characterized by the following steps: dispersing the aryl substituted o-diol compound, persulfate and sulfate in a solvent, and heating and refluxing until the reaction is complete to obtain an oxidative cleavage product which is a benzoic acid compound or a benzophenone compound;
the aryl substituted o-diol compound has the following general formula:
，
wherein R is 1 、R 2 、R 3 And R is 4 Independently are represented by phenyl, substituted phenyl or H, and R 1 、R 2 、R 3 And R is 4 At least one ofEach represents phenyl or substituted phenyl;
the persulfate refers to sodium persulfate;
the sulfate refers to copper sulfate pentahydrate.
2. The method for preparing a carbonyl compound by oxidative cleavage of an aryl-substituted o-diol according to claim 1, wherein the substituted phenyl group is a phenyl group substituted with 1 to 5 groups on the phenyl group, wherein the substituent on the phenyl group is an alkyl group, an alkoxy group or a halogen.
3. The method for producing a carbonyl compound by oxidative cleavage of an aryl-substituted o-diol according to claim 2, wherein the substituent on the phenyl group is in the para position of the o-diol.
4. The method for preparing carbonyl compounds by oxidative cleavage of aryl-substituted o-diols according to claim 1, wherein when R 1 And R is 2 When H is the same, R 3 And R is 4 The same; when R is 1 、R 2 、R 3 And R is 4 R when both are phenyl or substituted phenyl 1 And R is 2 Identical and R is 3 And R is 4 The same applies.
5. The method for producing a carbonyl compound by oxidative cleavage of an aryl-substituted o-diol according to claim 1, wherein the molar ratio of the aryl-substituted o-diol compound to persulfate is 1 (1.0-5.0).
6. The method for preparing a carbonyl compound by oxidative cleavage of an aryl-substituted o-diol according to claim 1, wherein the molar ratio of the aryl-substituted o-diol to the sulfate is 1 (0.01-1.0).
7. The method for producing a carbonyl compound by oxidative cleavage of an aryl-substituted o-diol according to claim 1, wherein the solvent is a mixed solvent of acetonitrile and water.
8. The method for producing a carbonyl compound by oxidative cleavage of an aryl-substituted o-diol according to claim 7, wherein the volume ratio of acetonitrile to water in the mixed solvent is 1 (0.1-10).
9. The method for preparing a carbonyl compound by oxidative cleavage of an aryl-substituted o-diol according to claim 1, wherein the mass to volume ratio of the aryl-substituted o-diol to the solvent is 1 (5-20).
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