CN114213372A - Catalytic synthesis method of anhydride - Google Patents
Catalytic synthesis method of anhydride Download PDFInfo
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- CN114213372A CN114213372A CN202111561402.5A CN202111561402A CN114213372A CN 114213372 A CN114213372 A CN 114213372A CN 202111561402 A CN202111561402 A CN 202111561402A CN 114213372 A CN114213372 A CN 114213372A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
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- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/32—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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Abstract
The invention belongs to the technical field of preparation of acid anhydride, and particularly relates to a method for preparing acid anhydride by catalytic dehydration of a carboxylic acid compound. The preparation method adopts N-N bidentate ligand as a catalyst, and the carboxylic acid compound is heated in an inert solvent to catalyze the intramolecular dehydration condensation of the carboxylic acid compound, so that the target anhydride compound is obtained with high yield. The invention has the advantages of simple catalytic system, good catalytic effect when the amount of the catalyst is small, and good substrate adaptability; the reaction speed is high, and the conversion rate is high; simple reaction operation and post-treatment steps, mild conditions, recyclable solvent for multiple times, no pollution in the reaction process and the like, can be widely used for production and application, and has great significance for the field of synthesis of carboxylic anhydride.
Description
Technical Field
The invention belongs to the technical field of preparation of acid anhydride, and particularly relates to a method for preparing acid anhydride by heating and dehydrating a carboxylic acid compound in an inert solvent by using an N-N bidentate ligand as a catalyst.
Background
The current classical anhydride preparation methods are mainly: heating and refluxing the charged water by acetic anhydride and heating and dehydrating at high temperature. The former method is delicate in post-treatment of acetic anhydride, difficult to completely remove the dry solvent, and due to the strong water absorption of acetic anhydride, the prepared acid anhydride is easy to absorb the moisture in the air and hydrolyze; the latter method usually requires more than 300 ℃, and the reaction conditions are harsh and difficult to realize in a large range.
In addition to these two classical anhydride production methods, japanese patent (JP2003146964) reports a method for producing an anhydride. Carboxylic acids are dehydrated in an inert solvent under catalytic amounts of acidic compounds such as the reported p-toluenesulfonic acid, trifluoromethanesulfonic acid, polyphosphoric acid, sulfuric acid, and the like. However, because of the general yield and the strong acidity of these acidic compounds, the metal reactors are subject to corrosion problems and thus cannot be widely used.
Sakakura, Akira et al also provide a process for preparing carboxylic anhydrides by synthesizing a complex phenylboronic acid catalyst to dehydrate phthalic acid under reflux in a solvent such as nonane, with better catalytic effect and higher yield (Sakakura, Akira et al, organic Letters,13(5),892-895, 2011; W02010103976). However, the reaction temperature is high, and the catalyst is expensive, complex and difficult to recover, so the economic cost is high, and industrialization is difficult to realize.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and the inventor invents a preparation method of anhydride, which comprises the steps of heating a carboxylic acid compound in an inert solvent under the condition of using an N-N bidentate ligand (such as 4, 7-diphenyl-1, 10-phenanthroline) as a catalyst, catalyzing the intramolecular dehydration condensation of the carboxylic acid compound, and obtaining a target anhydride compound with high yield. The method has the advantages of simple operation, mild reaction conditions, cheap and easily obtained raw materials and good yield.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a catalytic synthesis method of anhydride takes N-N bidentate ligand as a catalyst, a carboxylic acid compound is catalyzed to generate heating dehydration reaction in an inert solvent, and the corresponding anhydride compound is obtained after post-treatment after the reaction is finished;
wherein, the carboxylic acid compound refers to a compound having at least one dicarboxylic acid structure in which carboxylic acid groups are respectively bonded to two carbon atoms, that is, the carbon atoms to which the carboxylic acid groups are bonded are different carbon atoms.
Preferably, the carboxylic acid compound is a dicarboxylic acid compound or a tetracarboxylic acid compound.
Preferably, the dicarboxylic acid compound: at least one of the following compounds substituted or unsubstituted with a substituent: phthalic acid, cyclohexane-1, 2-dicarboxylic acid, cyclopentane-1, 2-dicarboxylic acid, succinic acid, glutaric acid, and the like.
Preferably, the tetracarboxylic acid compound: at least one of the following compounds substituted or unsubstituted with a substituent: pyromellitic acid, diphenyl ether-3, 3',4,4' -tetracarboxylic acid, diphenyl sulfone-3, 3',4,4' -tetracarboxylic acid, 4,4' - (hexafluoroisopropylene) diphthalic acid, and the like.
More preferably, the substituent is at least one of H, C1-C4 alkyl, C1-C4 alkoxy, C3-C6 cycloalkyl, halogen group (F, Cl, Br, I), nitro, cyano, C1-C4 alkylthio, aryl and the like; more preferably, the aryl group is at least one of phenyl, benzyl, and the like.
Preferably, the catalyst is an N-N bidentate ligand, more preferably at least one of a 1, 10-phenanthroline compound and a 2,2 '-bipyridyl compound, and the structural formula of the 1, 10-phenanthroline compound (shown in the left of formula I) or the 2,2' -bipyridyl compound (shown in the right of formula I) is shown in formula I;
wherein R is at least one of H, C1-C4 alkyl, C1-C4 alkoxy, halogen group (at least one of F, Cl, Br and I), amino, phenyl substituted by substituent and benzyl substituted by substituent; the substituent is at least one of H, C1-C4 alkyl, C1-C4 alkoxy, halogen group and nitro;
more preferably 4, 7-diphenyl-1, 10-phenanthroline.
Preferably, the molar ratio of the carboxylic acid compound to the catalyst is 1: (0.001-0.50).
The inert solvent is preferably a solvent which does not affect the reaction, and includes at least one of an aromatic solvent such as toluene or chlorobenzene, an ether solvent such as 1, 4-dioxane, a halogenated hydrocarbon solvent such as chloroform, a nitrile solvent such as acetonitrile, an alkane solvent such as heptane, and a solvent such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone. Under the condition of homogeneous composition, two or more solvents may be used alone or in combination.
Preferably, the mass ratio of the carboxylic acid compound to the solvent is preferably 1: (5-100), more preferably 1: 20.
preferably, the reaction temperature is in the range of 50-220 deg.C, more preferably 100-150 deg.C.
Preferably, the dehydration method is at least one of water separation of a water separator and dehydration of a drying agent. More preferably, the drying agent is at least one of molecular sieve, calcium chloride, magnesium sulfate and alumina.
Preferably, the reaction time is 2-48 h, and more preferably 4-20 h.
Preferably, the post-treatment is a conventional post-treatment operation, including solvent removal, drying, and the like.
Preferably, the reaction takes phthalic acid compounds as reaction raw materials, and the reaction formula is shown as follows:
compared with the prior art, the invention has the beneficial effects that:
(1) the substrate and the solvent are simple, economical and cheap, and the catalyst can be obtained by commercial means without complex process preparation.
(2) The invention utilizes the catalyst to catalyze the intramolecular dehydration condensation, has good substrate adaptability and simple catalytic system, has good catalytic effect when the catalyst amount is small, and has high reaction speed and extremely high conversion rate; the reaction operation and the post-treatment steps are simple, the conditions are mild, the solvent can be recycled for multiple times, and no by-product and no pollution are generated in the reaction process, so that the method can be widely used for production and application and has great significance for various fields needing carboxylic anhydride.
Detailed Description
The technical solution of the present invention is further clearly and completely described below by using specific examples, and it should be understood that the described examples of the present invention are implemented on the premise of the technical solution of the present invention, and detailed implementation and specific operation procedures are given, but only a part of examples of the present invention is provided, and not all examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified, and materials, reagents and the like used in the examples are commercially available unless otherwise specified. The products of the following examples were verified by common characterization methods such as nuclear magnetic resonance, and the verification results are consistent with the description of the present application.
Example 1: in a 25mL three-necked flask, 4, 7-diphenyl-1, 10-phenanthroline (84mg,10 mol%), phthalic acid (415mg,2.5mmol) were added, and finally, the solvents toluene (9mL) and N, N-dimethylacetamide (1mL) were added for solubilization, the mixture was heated under azeotropic reflux conditions for 12 hours, and the reflux was subjected to water removal by molecular sieves. After completion of the reaction, the reaction mixture was cooled and filtered, and the solvent was removed to obtain 366mg of phthalic anhydride with a yield of 99%.
The product obtained is1H NMR data are characterized as follows:1H NMR(500MHz,DMSO)δ8.12–8.07(m,2H)，8.03–7.99(m,2H)。
examples 2 to 3: the catalyst amount was reduced and the other reaction conditions were kept the same as in example 1.
Example 4: the reaction time and the amount of the catalyst are shortened, and other reaction conditions are consistent with those of example 1.
Examples 5 to 14: replacing the catalyst in example 1 with other phenanthroline derivative catalysts, and keeping other reaction conditions consistent with example 1.
Examples 15 to 18: the solvent in example 1 was changed and the other reaction conditions were kept the same as in example 1.
Examples 19 to 23: the phenanthroline catalyst in example 1 is replaced by a bipyridine derivative catalyst, and other reaction conditions are consistent with those in example 1.
Example 24: this example is a comparative example, with no catalyst added, and the other reaction conditions were the same as in example 1.
The conditions and results for examples 1 to 24 are shown in Table 1.
TABLE 1
Example 25: adding 4, 7-diphenyl-1, 10-phenanthroline (17mg, 2 mol%) and 4-methylphthalic acid (450mg, 2.5mmol) into a 25mL three-neck flask, finally adding solvents of toluene (9mL) and N, N-dimethylacetamide (1mL) for assisting dissolution, heating the mixture under an azeotropic reflux condition for 12 hours, and removing water from the reflux liquid through a molecular sieve. After the reaction, the reaction mixture was cooled, filtered and the solvent was removed to obtain 4-methylphthalic anhydride with a yield of 97%.
Examples 26 to 32: the carboxylic acid substrate of example 25 was replaced with other carboxylic acid compounds and other reaction conditions were kept the same as in example 25.
The conditions and results for the examples 25 to 32 are shown in Table 2.
TABLE 2
The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.
Claims (10)
1. A catalytic synthesis method of anhydride takes N-N bidentate ligand as a catalyst, a carboxylic acid compound is catalyzed to generate heating dehydration reaction in an inert solvent, and the corresponding anhydride compound is obtained after post-treatment after the reaction is finished;
wherein the carboxylic acid compound is a compound having at least one dicarboxylic acid structure in which carboxylic acid groups are bonded to two carbon atoms, respectively.
2. The method of claim 1, wherein the catalyst is an N-N bidentate ligand.
3. The catalytic synthesis method of acid anhydride according to claim 2, wherein the catalyst is at least one of 1, 10-phenanthroline compound or 2,2 '-bipyridine compound, and the structural formula of the 1, 10-phenanthroline compound or the 2,2' -bipyridine compound is shown in formula I;
wherein R is at least one of H, C1-C4 alkyl, C1-C4 alkoxy, halogen group, amino, phenyl substituted by substituent and benzyl substituted by substituent; the substituent is at least one of H, C1-C4 alkyl, C1-C4 alkoxy, halogen group and nitro.
4. The catalytic synthesis method of acid anhydride according to claim 2, wherein the catalyst is 4, 7-diphenyl-1, 10-phenanthroline.
5. The catalytic synthesis method of acid anhydride according to claim 1, wherein the molar ratio of the carboxylic acid compound to the catalyst is 1: (0.001-0.50).
6. The catalytic synthesis method of acid anhydride according to claim 1, wherein the inert solvent is at least one of aromatic solvent, ether solvent, halogenated hydrocarbon solvent, nitrile solvent, alkane solvent, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone
7. The catalytic synthesis method of acid anhydride according to claim 1, wherein the mass ratio of the carboxylic acid compound to the solvent is 1: (5-100).
8. The catalytic synthesis method of acid anhydride according to claim 1, wherein the reaction temperature is in the range of 50-220 ℃.
9. The catalytic synthesis method of acid anhydride according to claim 1, wherein the dehydration method is at least one of water separation of a water separator and dehydration of a drying agent.
10. The catalytic synthesis method of acid anhydride according to claim 1, wherein the reaction time is 2-48 h.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6310780A (en) * | 1986-07-02 | 1988-01-18 | Asahi Chem Ind Co Ltd | Production of aromatic cyclic acid anhydride |
| US4874558A (en) * | 1987-05-21 | 1989-10-17 | Indiana University Foundation | Polymer catalyzed synthesis of acid anhydrides |
| JP2001335571A (en) * | 2000-05-30 | 2001-12-04 | Nippon Nohyaku Co Ltd | Method for producing phthalic anhydride |
| CN101519407A (en) * | 2009-03-31 | 2009-09-02 | 复旦大学 | Synthesis method of cyclic acid anhydride capable of having substituent group |
| CN101668729A (en) * | 2006-12-15 | 2010-03-10 | 帝斯曼知识产权资产管理有限公司 | A kind ofly be used to prepare improving one's methods of substituted carboxylic acid anhydride |
| US20110319620A1 (en) * | 2009-03-11 | 2011-12-29 | National University Corporation Nagoya University | Method for producing carboxylic anhydride and arylboronic acid compound |
| JP2014166990A (en) * | 2013-01-31 | 2014-09-11 | Mitsubishi Chemicals Corp | METHOD FOR PRODUCING CARBOXYLIC ACID ANHYDRIDE AND METHOD FOR PRODUCING γ-BUTYROLACTONE |
| CN105330634A (en) * | 2015-12-07 | 2016-02-17 | 济南轩鸿生物医药有限公司 | One-pot method for preparing 3-hydroxyphtalic anhydride |
-
2021
- 2021-12-20 CN CN202111561402.5A patent/CN114213372B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6310780A (en) * | 1986-07-02 | 1988-01-18 | Asahi Chem Ind Co Ltd | Production of aromatic cyclic acid anhydride |
| US4874558A (en) * | 1987-05-21 | 1989-10-17 | Indiana University Foundation | Polymer catalyzed synthesis of acid anhydrides |
| JP2001335571A (en) * | 2000-05-30 | 2001-12-04 | Nippon Nohyaku Co Ltd | Method for producing phthalic anhydride |
| CN101668729A (en) * | 2006-12-15 | 2010-03-10 | 帝斯曼知识产权资产管理有限公司 | A kind ofly be used to prepare improving one's methods of substituted carboxylic acid anhydride |
| US20110319620A1 (en) * | 2009-03-11 | 2011-12-29 | National University Corporation Nagoya University | Method for producing carboxylic anhydride and arylboronic acid compound |
| CN101519407A (en) * | 2009-03-31 | 2009-09-02 | 复旦大学 | Synthesis method of cyclic acid anhydride capable of having substituent group |
| JP2014166990A (en) * | 2013-01-31 | 2014-09-11 | Mitsubishi Chemicals Corp | METHOD FOR PRODUCING CARBOXYLIC ACID ANHYDRIDE AND METHOD FOR PRODUCING γ-BUTYROLACTONE |
| CN105330634A (en) * | 2015-12-07 | 2016-02-17 | 济南轩鸿生物医药有限公司 | One-pot method for preparing 3-hydroxyphtalic anhydride |
Non-Patent Citations (3)
| Title |
|---|
| CARINE ROBERT 等: "Facile and Efficient Synthesis of Cyclic Anhydrides from Dicarboxylic Acids", 《ACS CATAL.》 * |
| MD. N. RASHED 等: "Heterogeneous catalysts for the cyclization of dicarboxylic acids to cyclic anhydrides as monomers for bioplastic production", 《GREEN CHEM.》 * |
| 刘福胜 等: "二元羧酸酐催化合成新工艺研究", 《化学与粘合》 * |
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