CN113234005A - Process for preparing 2-benzoylpyrrole - Google Patents
Process for preparing 2-benzoylpyrrole Download PDFInfo
- Publication number
- CN113234005A CN113234005A CN202110478080.1A CN202110478080A CN113234005A CN 113234005 A CN113234005 A CN 113234005A CN 202110478080 A CN202110478080 A CN 202110478080A CN 113234005 A CN113234005 A CN 113234005A
- Authority
- CN
- China
- Prior art keywords
- pyrrole
- reaction
- preparing
- benzoylpyrrole
- benzoyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- NFGGQMYSOLVBLF-UHFFFAOYSA-N phenyl(1h-pyrrol-2-yl)methanone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CN1 NFGGQMYSOLVBLF-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 20
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005751 Copper oxide Substances 0.000 claims abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000006480 benzoylation reaction Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000010 aprotic solvent Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 3
- 238000002360 preparation method Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010865 sewage Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AQIHMSVIAGNIDM-UHFFFAOYSA-N benzoyl bromide Chemical compound BrC(=O)C1=CC=CC=C1 AQIHMSVIAGNIDM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MWPIIMNHWGOFBL-UHFFFAOYSA-N dichloromethane;toluene Chemical compound ClCCl.CC1=CC=CC=C1 MWPIIMNHWGOFBL-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/333—Radicals substituted by oxygen or sulfur atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention relates to the technical field of a production method of 2-benzoyl pyrrole, in particular to a process for preparing 2-benzoyl pyrrole; the reaction steps are simplified, phosphorus oxychloride is not needed, the reaction is mild and controllable, the water consumption is reduced, and the generation of sewage is reduced; and dispersing pyrrole, copper oxide and a benzoylation reagent in a solvent, uniformly mixing, heating for reaction, and obtaining the 2-benzoylpyrrole after the reaction is finished.
Description
Technical Field
The invention relates to the technical field of a production method of 2-benzoyl pyrrole, in particular to a process for preparing 2-benzoyl pyrrole.
Background
As is known, publication No. CN103420889A discloses a method for synthesizing 2-benzoylpyrrole, and the technical key of the method is to remove the organic phase in the reaction solution. Compared with the prior art, the method has the advantages that: (1) standing and layering are not needed after demulsification; (2) the reaction condition is mild, and the operation is simple and convenient; (3) the purity of the product is greatly improved, and the content of the original crude product is directly improved to more than 98 percent without recrystallization; (4) the discharge amount of the waste water is reduced, the waste water treatment cost is reduced, and the method has an industrial application prospect; however, in the use process, phosphorus oxychloride is required to be added in the reaction process, so that the phosphorus content in the reaction by-products is increased, sewage is generated, the phosphorus oxychloride is vigorously fuming in humid air and is hydrolyzed into phosphoric acid and hydrogen chloride, the addition reaction in the production process is violent, a large potential safety hazard exists, and certain use limitation exists.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the process for preparing the 2-benzoyl pyrrole, which simplifies the reaction steps, does not need to use phosphorus oxychloride, has mild and controllable reaction, reduces the water consumption and reduces the generation of sewage.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a process for preparing 2-benzoylpyrrole: and dispersing pyrrole, copper oxide and a benzoylation reagent in a solvent, uniformly mixing, heating for reaction, and obtaining the 2-benzoylpyrrole after the reaction is finished.
Preferably, the reaction formula of the method is as follows:
preferably, the benzoylation reagent is selected from the group consisting of a benzoylhalide reagent and benzoic anhydride; benzoyl bromide and benzoyl chloride are preferred; most preferred is benzoyl chloride.
Preferably, the molar ratio of pyrrole to benzoylating agent is 1:1.0-1: 3.0; most preferably 1: 1.1.
preferably, the molar ratio of pyrrole to copper oxide is 1:0.1-1: 1.0; most preferably 1: 0.3.
Preferably, the reaction is carried out in a solvent selected from the group consisting of aprotic solvents, toluene, benzene, tetrahydrofuran, dichloromethane; toluene is most preferred.
Preferably, the mass ratio of the solvent to the pyrrole is (5-10): 1; most preferably 7.4: 1.
(III) advantageous effects
Compared with the prior art, the invention provides a process for preparing 2-benzoyl pyrrole, which has the following beneficial effects: the process for preparing 2-benzoyl pyrrole,
1. the reaction steps are simplified, and the production efficiency is improved;
2. phosphorus oxychloride is not used, so that the risk of the process is reduced, and the water consumption and the sewage yield are reduced;
3. the yield is improved by 10 to 15 percent compared with the traditional process of phosphorus oxychloride.
Detailed Description
Example 1
Pyrrole (1kg), copper oxide (0.4kg) and benzoyl chloride (2.3kg) were added to a toluene (7.4kg) solution in sequence, the temperature was raised to 60-70 ℃ for reaction for 6 hours, and the reaction was completed after confirming that benzoyl chloride disappeared by spotting. Filtering, adding water into the filtrate for separating liquid, extracting the water phase twice by using methylbenzene, combining the organic phases, adding anhydrous sodium sulfate for drying, filtering, concentrating under reduced pressure, adding 2 times of volume of n-heptane into the concentrate for decoloring, pulping and crystallizing to obtain 0.97kg of 2-benzoylpyrrole, wherein the molar yield is 80%.
1H NMR(400MHz,Chloroform-d)δ10.09(s,1H),8.27–7.78(m,2H),7.63–7.52(m,1H),7.48(ddd,J＝8.3,6.4,1.3Hz,2H),7.16(tt,J＝2.7,1.3Hz,1H),6.90(ddd,J＝3.9,2.5,1.3Hz,1H),6.34(dt,J＝3.9,2.5Hz,1H)。
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical scope of the present invention and the equivalent alternatives or modifications according to the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (9)
1. A process for preparing 2-benzoyl pyrrole is characterized in that pyrrole is used as a substrate, and the 2-benzoyl pyrrole is prepared by reaction in the presence of copper oxide and a benzoylation reagent.
2. The process for preparing 2-benzoylpyrrole according to claim 1, wherein the reaction formula of the process is as follows:
3. the process of claim 1, wherein the benzoylating reagent is selected from the group consisting of benzoylhalide and benzoic anhydride.
4. The process of claim 1, wherein the molar ratio of pyrrole to benzoylating agent is 1:1.0 to 1: 3.0.
5. The process of claim 1, wherein the molar ratio of pyrrole to copper oxide is from 1:0.1 to 1: 1.0.
6. The process of claim 1, wherein the reaction is carried out in a solvent selected from the group consisting of aprotic solvents, toluene, benzene, tetrahydrofuran, and dichloromethane.
7. The process for preparing 2-benzoylpyrrole according to claim 6, wherein the mass ratio of the solvent to pyrrole is (5-10): 1.
8. the process for preparing 2-benzoylpyrrole according to claim 1, wherein the reaction temperature is 40-110 ℃.
9. The process for the preparation of 2-benzoylpyrroles according to any one of claims 1 to 8, further comprising: after the reaction is finished, filtering, decompressing and concentrating, pulping and crystallizing to obtain the 2-benzoyl pyrrole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110478080.1A CN113234005A (en) | 2021-04-30 | 2021-04-30 | Process for preparing 2-benzoylpyrrole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110478080.1A CN113234005A (en) | 2021-04-30 | 2021-04-30 | Process for preparing 2-benzoylpyrrole |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113234005A true CN113234005A (en) | 2021-08-10 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110478080.1A Pending CN113234005A (en) | 2021-04-30 | 2021-04-30 | Process for preparing 2-benzoylpyrrole |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113234005A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584668A (en) * | 2012-02-27 | 2012-07-18 | 蚌埠中实化学技术有限公司 | Method for preparing 2,3-dibromo-5-benzoyl pyrrole |
-
2021
- 2021-04-30 CN CN202110478080.1A patent/CN113234005A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584668A (en) * | 2012-02-27 | 2012-07-18 | 蚌埠中实化学技术有限公司 | Method for preparing 2,3-dibromo-5-benzoyl pyrrole |
Non-Patent Citations (12)
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| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210810 |