CN117263788A - Synthesis of p-benzyl acetophenone by acetophenone one-step method - Google Patents
Synthesis of p-benzyl acetophenone by acetophenone one-step method Download PDFInfo
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- CN117263788A CN117263788A CN202310993342.7A CN202310993342A CN117263788A CN 117263788 A CN117263788 A CN 117263788A CN 202310993342 A CN202310993342 A CN 202310993342A CN 117263788 A CN117263788 A CN 117263788A
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- acetophenone
- benzyl
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- samarium
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- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- PPYJQGBEZQOXHC-UHFFFAOYSA-N 1-(4-benzylphenyl)ethanone Chemical compound C1=CC(C(=O)C)=CC=C1CC1=CC=CC=C1 PPYJQGBEZQOXHC-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 title description 11
- 230000015572 biosynthetic process Effects 0.000 title description 7
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 10
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 10
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940099607 manganese chloride Drugs 0.000 claims abstract description 10
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 10
- 239000011565 manganese chloride Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 238000005580 one pot reaction Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- -1 benzyl halide Chemical class 0.000 claims description 4
- 230000001737 promoting effect Effects 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims 1
- 229940073608 benzyl chloride Drugs 0.000 claims 1
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- XJTQJERLRPWUGL-UHFFFAOYSA-N iodomethylbenzene Chemical compound ICC1=CC=CC=C1 XJTQJERLRPWUGL-UHFFFAOYSA-N 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000012043 crude product Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000011541 reaction mixture Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000004440 column chromatography Methods 0.000 abstract 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- UAWABSHMGXMCRK-UHFFFAOYSA-L samarium(ii) iodide Chemical compound I[Sm]I UAWABSHMGXMCRK-UHFFFAOYSA-L 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000002696 manganese Chemical class 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000258 photobiological effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 102000009135 CB2 Cannabinoid Receptor Human genes 0.000 description 1
- 108010073376 CB2 Cannabinoid Receptor Proteins 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 102000016761 Haem oxygenases Human genes 0.000 description 1
- 108050006318 Haem oxygenases Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 108010025020 Nerve Growth Factor Proteins 0.000 description 1
- 102000007072 Nerve Growth Factors Human genes 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N benzopyrrole Natural products C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000007858 starting material 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a simple method for preparing p-benzyl acetophenone by using benzyl bromide and acetophenone in N, N-dimethylacetamide under the promotion of metal samarium and manganese chloride. Adding benzyl bromide and acetophenone into N, N-dimethylacetamide under stirring, and then sequentially adding metal samarium powder and manganese chloride powder. The reaction system is carried out under anhydrous and anaerobic conditions. Heating and stirring until the reaction is complete. The obtained reaction mixture was subjected to solvent recovery. The crude product is separated by column chromatography and the solvent is distilled off to obtain p-benzyl acetophenone with a yield of 60-70%.
Description
Technical Field
The invention belongs to the field of organic chemical synthesis, and particularly relates to a method for synthesizing p-benzyl acetophenone from acetophenone by one-step catalysis of lower manganese salt promoted by using metal samarium.
Background
P-benzyl acetophenone (shown in the following formula) has wide application as an organic synthesis reagent. The method can synthesize other bioactive substances with various structures through bromination reaction, and has important application in medicine. For example, p-benzyl acetophenone is used as a starting material to further synthesize a structure such as a nitrogen-containing five-membered heterocycle by a reaction such as bromination, and is used as a CB2 receptor [ document 1.Harnett,Jeremiah,WO2009071753 A1 2009-06-11], and is used in the medical field in the fields of neurotrophin-related disease research or heme oxygenase inhibition [ document 2.Ishikawa, junichi; et al, WO2010137350 A1 2010-12-02; roman, gheorghe; et al chemmed chem,2010,5 (9), 1541-1555 ], in addition, p-benzyl acetophenone and phenylhydrazine can form an indole heterocycle [ document 4.Samsoniya, sh. A.; et al, chemistry of Heterocyclic Compounds,2001,37 (7), 827-833 ]. P-benzyl acetophenone can also undergo oxidation or reduction reactions to produce a variety of useful products [ e.g., literature 5.Yi, hong; chemical Communications,2015,51 (74), 14046-14049, literature 6.Symeonidis,Theodoros S; photochemistry et al, photobiological Sciences,2015,14 (3), 563-568 ].
The method uses the p-halogenated acetophenone as a raw material, carries out coupling reaction with other reagents, and is a common method for synthesizing the p-benzyl acetophenone [ document 7.Hsu, che-Ming; journal of Organic Chemistry,2022,87 (5), 3799-3803, 8.pal, suman; advanced Synthesis & Catalysis,2016,358 (15), 2431-2435, literature 9.Lee, shao-Chi; et al organic Letters,2022,24 (1), 85-89 ]. The synthesis of p-benzyl acetophenone [ Ramakrishna, V.; in addition, p-benzyl acetophenone can be synthesized by acylation of diphenylmethane by acetyl chloride using a friedel-crafts acylation reaction [ document 10.Symeonidis,Theodoros S ]; photochemistry et al, photobiological Sciences,2015,14 (3), 563-568 ]. It is difficult to synthesize p-benzyl acetophenone in one step directly from acetophenone. The main reason is that acetophenone is a meta-position group, which is theoretically unfavorable for the formation of para-position products. This method has been rarely reported in literature until now, and individual literature reports that benzyl alcohol is coupled with acetophenone under specific conditions, the reaction effect is very poor [ literature 11.Wang, feng; chemical Communications,2008, (27), 3196-3198.Wang, feng; chemistry-A European Journal,2009,15 (3), 742-753 ] in this way only p-benzyl acetophenone was obtained in 15% yield.
Samarium is one of rare earth elements. Samarium diiodide has been very widely used in organic synthesis since its first introduction into organic synthesis by Kagan, a french chemist, 1980, and has been successfully applied to the synthesis of various natural products by promoting various types of chemical reactions and functional group conversions [ document 12. Szostank, m.; fazakerley, n.j.; parmar, d.; chemical Reviews,2014,114,5959-6039. However, samarium diiodide has some disadvantages in use, such as being very sensitive to air, so that long-term storage is difficult, and the samarium diiodide is generally prepared on the spot. On the other hand, samarium diiodide is used as a single electron transfer reagent, and only one electron is utilized during use. These limit their use in large scale preparations. In contrast, the samarium metal is stable in air, easy to operate, relatively inexpensive, and more electrons can be effectively utilized. Therefore, the direct application of the samarium metal to organic synthesis has better prospect. The rare earth resources are abundant in China, account for more than 90% of world reserves, and the development and utilization of the rare earth resources have great significance.
The invention discloses a method for preparing p-benzyl acetophenone by directly promoting one-step reaction of acetophenone and benzyl bromide by using samarium in the presence of manganese chloride, which is not reported in domestic and foreign documents.
Disclosure of Invention
The invention aims to provide a simple method for preparing p-benzyl acetophenone by using benzyl bromide and acetophenone with N, N-Dimethylacetamide (DMA) as a solvent under the promotion of samarium metal and manganese chloride.
The technical scheme of the invention is as follows:
in the presence of manganese salt, using samarium metal to deoxidize and couple benzyl bromide and acetophenone into p-benzyl acetophenone under the moderate condition of N, N-dimethyl acetamide (DMA), the reaction general formula is shown as follows:
wherein X=Cl, br, I
The technical scheme of the invention is as follows: adding benzyl bromide and acetophenone into N, N-dimethylacetamide which is dehydrated and dried in advance under stirring, and then sequentially adding metal samarium powder and manganese chloride powder. Wherein the dosage of samarium powder is 0.5-5 times of the molar ratio of acetophenone dosage; the manganese chloride dosage is 0.1-1 times of the samarium powder dosage in terms of molar ratio; the dosage of the N, N-dimethylacetamide is 5-50 times of the acetophenone; the reaction system is carried out under anhydrous and anaerobic conditions.
Heating to a certain temperature, and stirring until the reaction is complete. The obtained reaction mixture is subjected to solvent recovery, the residue is subjected to post-treatment, and chromatographic column separation is carried out to obtain the pure p-benzyl acetophenone product with the yield of 60-70%.
The invention has the advantages and positive effects that: the synthetic route is simple and efficient, the p-benzyl acetophenone can be obtained through one-step reaction, the operation steps are few, the intermediate does not need to be separated, and the operation requirement is greatly simplified; the p-benzyl acetophenone compound synthesized by the method has high yield, simple post-treatment process and easy separation during post-treatment of the product; the reaction condition of the invention is easy to realize, and the special requirements of strong acid, strong alkali, strong toxicity, illumination, biocatalysis and the like are avoided; the raw materials of the invention are simple and easy to obtain, the used benzyl bromide and manganese salt have low cost, are all basic chemical products, are easy to obtain, and are relatively friendly to the environment; the samarium metal is rare earth metal, and the rare earth resource of China occupies the first place of the world, so that the effective development and utilization of the rare earth metal has great significance to China; the solvent N, N-dimethylacetamide used in the invention can be fully recovered and reused, and thus the reaction cost is further reduced.
Detailed Description
The following synthesis examples serve to further illustrate the invention but are not meant to limit it.
Example 1
To a three-necked flask, anhydrous N, N-dimethylacetamide (5 mL) was added, followed by benzyl bromide (0.3 mL) and acetophenone (0.3 mL), and manganese chloride (0.13 g) and samarium powder (0.3 g) were sequentially added under magnetic stirring. Slowly heating to 50 ℃ under the protection of nitrogen, and stirring and reacting for 4h. 5mL of diluted hydrochloric acid (2 mol. L) -1 ) Terminating the reaction, performing post-treatment on the reaction mixture to obtain a crude product, and further purifying the crude product by a chromatographic column to obtain the p-benzyl acetophenone with the yield of 67%.
A colorless oil; 1 H NMR(500MHz,Chloroform-d)δ7.88(m,2H),7.28(m,4H),7.24-7.21(m,1H),7.17(m，2H),4.02(s,2H),2.56(s,3H)ppm； 13 C NMR(125MHz,Chloroform-d)δ197.75,146.82,140.07,135.32,129.13,128.96,128.66,126.44,41.93,26.54ppm。
Claims (4)
1. a simple method for synthesizing p-benzyl acetophenone is characterized in that in the presence of manganese chloride, metal samarium is used for promoting one-step reaction of benzyl halide and acetophenone in N, N-dimethylacetamide to prepare p-benzyl acetophenone, and the preparation process comprises the following steps:
the benzyl halide and acetophenone are mixed uniformly in N, N-dimethylacetamide which is dehydrated and dried in advance, and then the samarium metal powder and the manganese chloride powder are added in sequence. Stirring under nitrogen protection at a certain temperature until the reaction is complete. And (3) recovering the solvent of the obtained reaction mixed solution, and separating the residue by a chromatographic column after post-treatment to obtain the p-benzyl acetophenone pure product.
2. The simple method for synthesizing p-benzyl acetophenone according to claim 1, wherein the amount of benzyl bromide is 0.5-5 times of the molar ratio of acetophenone; the dosage of samarium powder is 0.5-5 times of the molar ratio of acetophenone dosage; the manganese chloride dosage is 0.1-1 times of the samarium powder dosage in terms of molar ratio; the dosage of the N, N-dimethylacetamide is 5-50 times of the acetophenone.
3. The simple process for synthesizing p-benzyl acetophenone according to claim 1, wherein the benzyl halide is one or more of benzyl chloride, benzyl bromide and benzyl iodide.
4. The simple method for synthesizing p-benzyl acetophenone according to claim 1, wherein the reaction temperature is 0-100 ℃, the reaction is one-pot one-step reaction, the reaction solvent can be recovered, and the reaction yield is 60-70%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310993342.7A CN117263788A (en) | 2023-08-08 | 2023-08-08 | Synthesis of p-benzyl acetophenone by acetophenone one-step method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310993342.7A CN117263788A (en) | 2023-08-08 | 2023-08-08 | Synthesis of p-benzyl acetophenone by acetophenone one-step method |
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| Publication Number | Publication Date |
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| CN117263788A true CN117263788A (en) | 2023-12-22 |
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| CN202310993342.7A Pending CN117263788A (en) | 2023-08-08 | 2023-08-08 | Synthesis of p-benzyl acetophenone by acetophenone one-step method |
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| CN (1) | CN117263788A (en) |
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- 2023-08-08 CN CN202310993342.7A patent/CN117263788A/en active Pending
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