CN117105979A - Method for synthesizing photocatalysis beta-keto diaryl phosphine oxide compound - Google Patents
Method for synthesizing photocatalysis beta-keto diaryl phosphine oxide compound Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 11
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- -1 phosphine oxide hydrogen compounds Chemical class 0.000 claims abstract description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 81
- 238000002360 preparation method Methods 0.000 claims description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 24
- 239000012074 organic phase Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 17
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 239000003480 eluent Substances 0.000 claims description 12
- 238000004809 thin layer chromatography Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 229930187593 rose bengal Natural products 0.000 claims description 9
- 229940081623 rose bengal Drugs 0.000 claims description 9
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 claims description 9
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- 101100438134 Rattus norvegicus Cabs1 gene Proteins 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- VDNLFJGJEQUWRB-UHFFFAOYSA-N rose bengal free acid Chemical group OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C(O)=C(I)C=C21 VDNLFJGJEQUWRB-UHFFFAOYSA-N 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 abstract description 8
- 238000006114 decarboxylation reaction Methods 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
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- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- 238000006366 phosphorylation reaction Methods 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 description 8
- VWBYXJRDIQCSLW-UHFFFAOYSA-N O=[P](c1ccccc1)c1ccccc1 Chemical compound O=[P](c1ccccc1)c1ccccc1 VWBYXJRDIQCSLW-UHFFFAOYSA-N 0.000 description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 8
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 7
- WBYWAXJHAXSJNI-VOTSOKGWSA-N trans-cinnamic acid Chemical compound OC(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-N 0.000 description 7
- VCPZZWOAQNHOLZ-UHFFFAOYSA-N 2-diphenylphosphoryl-1-phenylethanone Chemical compound C=1C=CC=CC=1C(=O)CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VCPZZWOAQNHOLZ-UHFFFAOYSA-N 0.000 description 6
- 238000010276 construction Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 4
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 150000003003 phosphines Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QNKQTUDXHFLEAL-UHFFFAOYSA-N 1-(4-chlorophenyl)-2-diphenylphosphorylethanone Chemical compound ClC1=CC=C(C=C1)C(CP(=O)(C1=CC=CC=C1)C1=CC=CC=C1)=O QNKQTUDXHFLEAL-UHFFFAOYSA-N 0.000 description 2
- GCUWBTGMXUIKOB-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)phosphonoylbenzene Chemical compound C1=CC(C)=CC=C1P(=O)C1=CC=C(C)C=C1 GCUWBTGMXUIKOB-UHFFFAOYSA-N 0.000 description 2
- GXLIFJYFGMHYDY-ZZXKWVIFSA-N 4-chlorocinnamic acid Chemical compound OC(=O)\C=C\C1=CC=C(Cl)C=C1 GXLIFJYFGMHYDY-ZZXKWVIFSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000006130 Horner-Wadsworth-Emmons olefination reaction Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
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- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ZBEDLGKSWBORBS-UHFFFAOYSA-N 1,3,2-dioxaborolan-2-ol Chemical class OB1OCCO1 ZBEDLGKSWBORBS-UHFFFAOYSA-N 0.000 description 1
- PIAOLBVUVDXHHL-UHFFFAOYSA-N 2-nitroethenylbenzene Chemical class [O-][N+](=O)C=CC1=CC=CC=C1 PIAOLBVUVDXHHL-UHFFFAOYSA-N 0.000 description 1
- RURHILYUWQEGOS-VOTSOKGWSA-N 4-Methylcinnamic acid Chemical compound CC1=CC=C(\C=C\C(O)=O)C=C1 RURHILYUWQEGOS-VOTSOKGWSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 108090000204 Dipeptidase 1 Proteins 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- BZRLFVYTFDNRJT-UHFFFAOYSA-N [P]C=C Chemical class [P]C=C BZRLFVYTFDNRJT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 102000006635 beta-lactamase Human genes 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 230000004097 bone metabolism Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005686 cross metathesis reaction Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical class C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention provides a method for synthesizing a photocatalysis beta-keto diaryl phosphine oxide compound, which takes unsaturated carboxylic acid and phosphine oxide hydrogen compounds as raw materials, visible light as a light source, organic dye as a catalyst and no other additives are used, and the following reaction is carried out in a solvent DMSO. The method takes visible light catalysis as a means, and organic dye is subjected to decarboxylation coupling under the catalysis of a photocatalyst to construct a C-P bond to synthesize the beta-ketodiaryl phosphine oxide compound. The visible light utilized by the invention is rich in storage in nature and convenient to use, and is a green energy source which is low in cost, clean and pollution-free; the phosphorylation reaction system has no metal, no extra additive and no inert gas protection, and the post-treatment is simple and the operation is simple; the reaction device is simple, the condition is mild, the reaction can be realized at a lower temperature, the energy consumption is saved, and meanwhile, the target product can be obtained with a higher yield.
Description
Technical Field
The invention belongs to the technical field of organic matter synthesis, and particularly relates to a method for synthesizing a photocatalysis beta-keto diaryl phosphine oxide compound.
Background
Beta-ketodiaryl phosphine oxide as one kind of important organic compound containing phosphorus has wide application in organic chemistry, coordination chemistry, biochemistry and other fields and is one kind of valuable organic compound. Beta-ketodiaryl phosphine oxides are very versatile intermediates in organic chemistry, in particular for the construction of alpha, beta-unsaturated carbonyl compounds by the Horner-Wadsworth-Emmons (HWE) reaction. In organic synthesis, beta-ketodiaryl phosphine oxide is an important organic synthon, and various important derivatives can be obtained through a series of conversion; in coordination chemistry, beta-ketodiaryl phosphine oxide plays an important role as a common organic phosphine ligand, and can be used as a multifunctional precursor in the organic synthesis process and can also be used as a potential ligand of various complexes due to the coordination property of the beta-ketodiaryl phosphine oxide. In biochemistry, beta-ketodiaryl phosphine oxides can be used as useful precursors for synthesizing chiral beta-amino and beta-hydroxy phosphonic acids due to their wide range of biological activities. In addition, the beta-ketodiaryl phosphine oxide derivative can play an important role in resisting cancer, promoting bone metabolism and inhibiting beta-lactamase activity.
Diphenyl phosphine oxide is an important organic synthesis intermediate, is widely used for synthesizing various pesticides and chiral phosphine ligands, and can replace alkali metal cyanide as a coupling agent for synthesizing heterocyclic compounds. The alpha-beta-unsaturated carboxylic acid can provide an alkenyl synthon in the coupling reaction, and can be subjected to coupling reaction with various phosphine oxidizing reagents to synthesize the unique structure of various alkenyl phosphino compounds, and the alpha-beta-unsaturated carboxylic acid is an important intermediate in the organic synthesis, has the advantages of easy preparation, low price, good stability, easy storage and transportation and the like, and the final byproducts are carbon dioxide and water in the reaction process, so that the preparation method is very environment-friendly and meets the current requirements of green chemistry. Therefore, the coupling reaction can be carried out by substituting sensitive (or active) reagents such as organic metals. Meanwhile, after the decarboxylation coupling reaction of the alpha-beta-unsaturated carboxylic acid, the post-reaction treatment is simple, and the method has the advantages of high-efficiency three-dimensional and regioselectivity in the reaction process and the like. In view of the above, the decarboxylation coupling reactions involving α - β -unsaturated carboxylic acids are of increasing interest to the chemist. In recent years, the decarboxylation of alpha-beta-unsaturated carboxylic acids with transition metals to build up alkenylphosphine oxidation has become a hotspot in current organic phosphine chemistry research.
Phosphine oxide compounds are important chemical intermediates, and in recent years, alkyl phosphine oxide organic compounds are widely discovered and applied to the fields of bioactive molecules, medicines (medicines and pesticides), novel high-molecular functional materials and the like, and are increasingly paid attention to by organic scientists. These compounds can be prepared by olefin cross-metathesis or Heck-type coupling. However, these methods have problems such as limited substrate range, unsatisfactory noble metal catalyst and productivity. In addition, reported routes to synthesize such building blocks also include cross-coupling of P (O) H compounds with alkenyl derivatives (e.g., olefins, ethylene halides, ethylene sulfides, ethylene borates, β -nitrostyrenes, vinyl tetrafluoroborates, and addition of P (O) H compounds to alkynes), but most methods are limited, including the use of unsaturated olefins or alkynes, are generally expensive and have poor air stability, relatively aggressive conditions (strong and high temperatures), and low stereoselectivity. From the above point of view, it is still necessary to develop a new synthesis scheme for vinyl phosphorus compounds. On the other hand, alkenoic acids are one of the most attractive components in organic synthesis, are generally insensitive to air and moisture, and are easy to transport and store. Their unique configuration ensures the stereoselectivity of the reaction. Thus, decarboxylation of alkenyl acids has shown wide application in various bond-forming reactions of C-C, C-N, C-S. The alpha-beta unsaturated carboxylic acid is cheap and easy to obtain, convenient to prepare, and has the characteristics of high reaction selectivity, good functional group compatibility and the like. Therefore, the catalyst can replace an organic metal reagent or an organic boron (organic silicon) reagent to participate in the reaction as a synthon, and in the reaction process, alpha-beta unsaturated carboxylic acid decarboxylation can provide a dilute radical synthon, and the dilute radical synthon is coupled with a phosphine oxide alkyl reagent to obtain different alkenyl phosphine oxide compounds. Thus, the decarboxylation synthesis of alkenylphosphine oxides from α - β unsaturated carboxylic acids is a hotspot of interest and research by organophosphine chemists today.
In view of the importance of organic phosphine compounds, how to construct C-P bonds with high efficiencyRealizing the diversity synthesis of the organic phosphine compound is always one of the important research points and hot spots in the field of organic synthesis. Traditional synthetic methods for organic phosphine compounds rely mainly on the conversion of inorganic phosphorus-containing reagents, such as P 4 、PCl 3 、PH 3 And the like, not only requires a longer reaction step, but also such reagents are generally poor in stability and difficult to store and apply, and the reaction often requires an active metal reagent and severe reaction conditions, generates waste with equivalent mass, and is difficult to obtain high atomic economy and step economy.
The organic phosphine compound has various structures and can provide a wide substrate range, so that the organic phosphine compound is directly utilized as a raw material, and the construction of the organic phosphine compound by cutting off the C-P bond is a relatively economical and direct choice. Currently, various methods have been used for cleavage and recombination of C-P bonds, including transition metal catalysis, photocatalysis, and other reagent-mediated methods.
The development of photocatalysis provides a brand new idea for green sustainable chemical reaction, and as a synthesis strategy, construction of various chemical bonds is realized, and the reaction is characterized by mild conditions, high atom economy and good functional group compatibility. The photocatalysis synthesis technology can realize the rupture and recombination of chemical bonds under mild conditions by utilizing the energy of light, opens up a new path for the construction of C-P bonds and the synthesis of organic phosphine compounds, and is also the most popular research hot spot at present.
Disclosure of Invention
First, the technical problem to be solved
The invention provides a method for synthesizing a photocatalysis beta-keto diaryl phosphine oxide compound, which aims to solve the technical problem of how to synthesize the beta-keto diaryl phosphine oxide compound in a green and economical way.
(II) technical scheme
In order to solve the technical problems, the invention provides a synthesis method of a photocatalysis beta-keto diaryl phosphine oxide compound, which comprises the following steps of taking unsaturated carboxylic acid and phosphine oxide hydrogen compound as raw materials, taking visible light as a light source, taking organic dye as a catalyst, and not using other additives, and carrying out the following reaction in a solvent DMSO:
wherein R is 1 Is Ph, CH 3 Ph、MeOPh、Cl、Br、CF 3 、NO 2 Ph, py or Nap; r is R 2 Is Ph, CH 3 Ph、MeOPh、ClPh、BrPh、CF 3 Ph、NO 2 Ph, py or Nap;
and (3) carrying out post-treatment on the reaction liquid to obtain the beta-ketodiaryl phosphine oxide compound.
Further, a white LED is used as a light source of visible light.
Further, rose bengal or eosin is used as the organic dye.
Further, the mol ratio of unsaturated carboxylic acid to phosphine oxide hydrogen compound to organic dye is 1:4 (0.01-0.05), the reaction temperature is 25-50 ℃, the stirring is continuous, the light source of visible light is 25-30W, and the reaction time is 24 hours.
Further, the post-treatment process is that the reaction liquid is moved into a separating funnel, 15mL of water is added, ethyl acetate is used for extraction, the organic phases are combined, then the saturated NaCl solution is used for water washing, the organic phases are concentrated by a rotary evaporator to obtain crude products, and then the crude products are separated to obtain target products.
Further, when ethyl acetate was used for extraction, 15mL ethyl acetate was used each time for extraction 3 times.
Further, separation is performed using a thin layer chromatography preparation plate or a flash preparation chromatograph.
Further, the volume ratio of the eluent adopted in the separation process is ethyl acetate to n-hexane=2:1.
(III) beneficial effects
The invention provides a method for synthesizing a photocatalysis beta-keto diaryl phosphine oxide compound, which takes unsaturated carboxylic acid and phosphine oxide hydrogen compounds as raw materials, visible light as a light source, organic dye as a catalyst and no other additives are used, and the following reaction is carried out in a solvent DMSO. The method takes visible light catalysis as a means, and organic dye is subjected to decarboxylation coupling under the catalysis of a photocatalyst to construct a C-P bond to synthesize the beta-ketodiaryl phosphine oxide compound. The visible light utilized by the invention is rich in storage in nature and convenient to use, and is a green energy source which is low in cost, clean and pollution-free; the phosphorylation reaction system has no metal, no extra additive and no inert gas protection, and the post-treatment is simple and the operation is simple; the reaction device is simple, the condition is mild, the reaction can be realized at a lower temperature, the energy consumption is saved, and meanwhile, the target product can be obtained with a higher yield.
Detailed Description
To make the objects, contents and advantages of the present invention more apparent, the following detailed description of the present invention will be given with reference to examples.
Example 1
Preparation of 2- (Diphenyl) -1-phenyl ethane-1-one
A10 mL reaction tube was placed in a magnetic stirrer, trans-cinnamic acid (0.2 mmol,29.6 mg), diphenylphosphorus oxide (0.8 mmol,161.8 mg) and rose bengal (0.006mmol, 6.1 mg) were added sequentially, then 1.5mL of LDMSO was added, and the reaction tube was placed in a white LED and heated to 40℃for irradiation for 24 hours (the reaction tube was kept 8cm from the LED). After the reaction, transferring the reaction solution into a separating funnel, adding 15mL of water, extracting with ethyl acetate (15 mL multiplied by 3 times), merging organic phases, washing with saturated NaCl solution, concentrating the organic phases by a rotary evaporator to obtain a crude product, and separating by adopting a thin-layer chromatography preparation plate or a rapid preparation chromatograph (the volume ratio of eluent is ethyl acetate: n-hexane=2:1), thus obtaining 75% of target product 2- (Diphenylphosphoryl) -1-phenylethan-1-one.
2- (Diphenyl) phospho) -1-phenyl ethane-1-one was a white solid with 75% yield.
1 H NMR(ppm,Chloroform-d)δ7.90(d,2H,J＝8.0Hz),7.74(dd,4H,J＝8.0,12.0Hz),7.47-7.19(m,10H),4.14(d,2H,J＝16.0Hz).
13 C NMR(ppm,Chloroform-d)δ192.8,136.8,133.7,132.3,132.2,131.2,131.1,129.2,128.7,128.6,128.5,29.7.
HRMS(ESI)calcd for C 20 H 17 NaO 2 P(M+Na) + :343.3175；found:343.3175.
IR(cm -1 )：3010，2932，2851，1698，1598，1463，1380，1345，1025，1001，7532，658.
Example 2
Preparation of 2- (Diphenyl) -1-phenyl ethane-1-one
10mL of the reaction tube was placed in a magnetic stirrer, trans-cinnamic acid (0.2 mmol,29.6 mg), diphenylphosphorus oxide (0.8 mmol,161.8 mg) and eosin (0.006mmol, 4.2mg, 3%) were sequentially added, then 1.5mL of the MSO was added, and the reaction tube was placed in a white LED and heated to 40℃for irradiation for 24 hours (the reaction tube was kept at a distance of 8cm from the LED). After the reaction, transferring the reaction solution into a separating funnel, adding 15mL of water, extracting with ethyl acetate (15 mL multiplied by 3 times), merging organic phases, washing with saturated NaCl solution, concentrating the organic phases by a rotary evaporator to obtain a crude product, and separating by adopting a thin-layer chromatography preparation plate or a rapid preparation chromatograph (the volume ratio of eluent is ethyl acetate: n-hexane=2:1), thus obtaining 64% of target product 2- (Diphenylphosphoryl) -1-phenylethan-1-one.
The product identification parameters were the same as in example 1.
Example 3
10mL of the reaction tube was placed in a magnetic stirrer, trans-cinnamic acid (0.2 mmol,29.6 mg), diphenylphosphorus oxide (0.8 mmol,161.8 mg) and eosin (0.002mmol, 1.4mg, 1%) were sequentially added, then 1.5mL of the MSO was added, and the reaction tube was placed in a white LED and heated to 40℃for irradiation for 24 hours (the reaction tube was kept at a distance of 8cm from the LED). After the reaction, transferring the reaction solution into a separating funnel, adding 15mL of water, extracting with ethyl acetate (15 mL multiplied by 3 times), merging organic phases, washing with saturated NaCl solution, concentrating the organic phases by a rotary evaporator to obtain a crude product, and separating by adopting a thin-layer chromatography preparation plate or a rapid preparation chromatograph (the volume ratio of eluent is ethyl acetate: n-hexane=2:1), thus obtaining 21% of target product 2- (Diphenylphosphoryl) -1-phenylethan-1-one.
The product identification parameters were the same as in example 1.
Example 4
10mL of the reaction tube was placed in a magnetic stirrer, trans-cinnamic acid (0.2 mmol,29.6 mg), diphenylphosphorus oxide (0.8 mmol,161.8 mg) and eosin (0.01 mmol,6.9mg, 5%) were sequentially added, then 1.5mL of DMSO was added, and the reaction tube was placed in a white LED and heated to 40℃for irradiation for 24 hours (the reaction tube was kept 8cm from the LED). After the reaction, transferring the reaction solution into a separating funnel, adding 15mL of water, extracting with ethyl acetate (15 mL multiplied by 3 times), merging organic phases, washing with saturated NaCl solution, concentrating the organic phases by a rotary evaporator to obtain a crude product, and separating by adopting a thin-layer chromatography preparation plate or a rapid preparation chromatograph (the volume ratio of eluent is ethyl acetate: n-hexane=2:1), thus obtaining 21% of target product 2- (Diphenylphosphoryl) -1-phenylethan-1-one.
Example 5
Preparation of 2- (Diphenyl) -1-phenyl ethane-1-one
A10 mL reaction tube was placed in a magnetic stirrer, trans-cinnamic acid (0.2 mmol,29.6 mg), diphenylphosphorus oxide (0.8 mmol,161.8 mg) and rose bengal (0.006mmol, 6.1 mg) were added sequentially, then 1.5mL of LDMSO was added, and the reaction tube was placed in a white LED and heated to 25℃for irradiation for 24 hours (the reaction tube was kept 8cm from the LED). After the reaction, transferring the reaction solution into a separating funnel, adding 15mL of water, extracting with ethyl acetate (15 mL multiplied by 3 times), merging organic phases, washing with saturated NaCl solution, concentrating the organic phases by a rotary evaporator to obtain a crude product, and separating by adopting a thin-layer chromatography preparation plate or a rapid preparation chromatograph (the volume ratio of eluent is ethyl acetate: n-hexane=2:1), thus obtaining the 35% target product 2- (Diphenylphosphoryl) -1-phenylethan-1-one.
The product identification parameters were the same as in example 1.
Example 6
Preparation of 2- (Diphenyl) -1-phenyl ethane-1-one
A10 mL reaction tube was placed in a magnetic stirrer, trans-cinnamic acid (0.2 mmol,29.6 mg), diphenylphosphorus oxide (0.8 mmol,161.8 mg) and rose bengal (0.006mmol, 6.1 mg) were added sequentially, then 1.5mL of LDMSO was added, and the reaction tube was placed in a white LED and heated to 50deg.C for irradiation for 24 hours (the reaction tube was kept 8cm from the LED). After the reaction, transferring the reaction solution into a separating funnel, adding 15mL of water, extracting with ethyl acetate (15 mL multiplied by 3 times), merging organic phases, washing with saturated NaCl solution, concentrating the organic phases by a rotary evaporator to obtain a crude product, and separating by adopting a thin-layer chromatography preparation plate or a rapid preparation chromatograph (the volume ratio of eluent is ethyl acetate: n-hexane=2:1), thus obtaining 65% of target product 2- (Diphenylphosphoryl) -1-phenylethan-1-one.
The product identification parameters were the same as in example 1.
Example 7
Preparation of 2- (Diphenyl) phosphinyl-1- (p-tolyl) ethane-1-one
10mL of the reaction tube was placed in a magnetic stirrer, 4-methyl cinnamic acid (0.2 mmol,32.4 mg), diphenyl phosphorus oxide (0.8 mmol,161.8 mg) and rose bengal (0.006mmol, 6.1 mg) were sequentially added, then 1.5mL of LDMSO was added, and the reaction tube was placed in a white LED and heated to 40℃and irradiated for 24 hours (the reaction tube was kept at a distance of 8cm from the LED). After the reaction, transferring the reaction solution into a separating funnel, adding 15mL of water, extracting with ethyl acetate (15 mL multiplied by 3 times), merging organic phases, washing with saturated NaCl solution, concentrating the organic phases by a rotary evaporator to obtain a crude product, and separating by adopting a thin-layer chromatography preparation plate or a rapid preparation chromatograph (the volume ratio of eluent is ethyl acetate: n-hexane=2:1), thus obtaining the target product 2- (diphylphosphoryl) -1- (p-tolyl) ethane-1-one.
2- (Diphenyl) -1- (p-tolyl) ethane-1-one was a white solid in 78% yield.
1 H NMR(ppm,Chloroform-d)δ7.81-7.71(m,6H),7.46-7.19(m,6H),7.14(d,2H,J＝8.0Hz),4.08(d,2H,J＝16.0Hz),2.31(s,3H).
13 C NMR(ppm,Chloroform-d)δ192.3,176.1,144.7,137.0,134.4,132.3,132.2,131.3,131.2,129.4,129.3,128.7,128.6,29.7,21.7,20.7.
HRMS(ESI)calcd for C 21 H 19 NaO 2 P(M+Na) + :357.3445；found:357.3446.
IR(cm -1 )：3025，2901，2812，1692，1589，1465，1385，1365，1051，1007，751，618.
Example 8
Preparation of 1- (4-Chlorophenyl) -2- (diphenylphosphoryl) ethane-1-one
10mL of the reaction tube was placed in a magnetic stirrer, 4-chlorocinnamic acid (0.2 mmol,36.5 mg), diphenylphosphorus oxide (0.8 mmol,161.8 mg) and rose bengal (0.006mmol, 6.1 mg) were sequentially added, then 1.5mL of LDMSO was added, and the reaction tube was placed in a white LED and heated to 40℃and irradiated for 24 hours (the reaction tube was kept at a distance of 8cm from the LED). After the reaction, transferring the reaction solution into a separating funnel, adding 15mL of water, extracting with ethyl acetate (15 mL multiplied by 3 times), merging organic phases, washing with saturated NaCl solution, concentrating the organic phases by a rotary evaporator to obtain a crude product, and separating by adopting a thin-layer chromatography preparation plate or a rapid preparation chromatograph (the volume ratio of eluent is ethyl acetate: n-hexane=2:1), thus obtaining the target product 1- (4-Chlorophenyl) -2- (diphenyylphosphoryl) ethane-1-one.
1- (4-Chlorophenyl) -2- (diphenylphosphinoyl) ethane-1-one was a white solid in 76% yield.
1 H NMR(ppm,Chloroform-d)δ7.95(d,2H,J＝8.0Hz),7.79(dd,4H,J＝8.0,12.0Hz),7.56-7.38(m,8H),4.14(d,2H,J＝16.0Hz)；
13 C NMR(ppm,Chloroform-d)δ192.8,175.7,136.8,133.7,132.3,132.2,131.2,131.1,129.2,128.7,128.6,128.5,29.7.
HRMS(ESI)calcd for C 20 H 16 ClNaO 2 P(M+Na) + :377.7595；found:377.7778.
IR(cm -1 )：3008，2988，2835，1749，1581，1453，1371，1312，1016，999，752，618.
Example 9
Preparation of 2- (di-p-Tolylphosphoryl) -1-phenylethan-1-one
10mL of the reaction tube was placed in a magnetic stirrer, trans-cinnamic acid (0.2 mmol,29.6 mg), bis (p-methylphenyl) phosphine oxide (0.8 mmol,184.2 mg) and rose bengal (0.006mmol, 6.1 mg) were sequentially added, then 1.5mL of DMSO was added, and the reaction tube was placed in a white LED and heated to 40℃and irradiated for 24 hours (the reaction tube was kept 8cm from the LED). After the reaction, transferring the reaction solution into a separating funnel, adding 15mL of water, extracting with ethyl acetate (15 mL multiplied by 3 times), merging organic phases, washing with saturated NaCl solution, concentrating the organic phases by a rotary evaporator to obtain a crude product, and separating by adopting a thin-layer chromatography preparation plate or a rapid preparation chromatograph (the volume ratio of eluent is ethyl acetate: n-hexane=2:1), thus obtaining the target product 2- (di-p-Tolylphosphoryl) -1-phenylethan-1-one.
2- (di-p-Tolylphosphoryl) -1-phenylethane-1-one was a colourless oil in 71% yield.
1 H NMR(ppm,Chloroform-d)δ7.87(d,2H,J＝8.0Hz),7.56(dd,4H,J＝8.0,12.0Hz),7.31(d,2H,J＝8.0Hz),7.20-7.19(m,5H),4.05(d,2H,J＝16.0Hz),2.31(s,6H).
13 C NMR(ppm,Chloroform-d)δ191.9,142.8,140.2,135.3,131.3,131.0,130.8,129.9,129.5,129.3,128.8,29.7,21.6.
HRMS(ESI)calcd for C 22 H 21 ClNaO 2 P(M+Na) + :371.3175；found:371.3175.
IR(cm -1 )：3015，2931，2863，1755，1586，1455，1388，1368，,1119，1002，758，638。
Example 10
Preparation of 1- (4-Chlorophenyl) -2- (di-p-tolylphosphoryl) ethane-1-one
10mL of the reaction tube was placed in a magnetic stirrer, 4-chlorocinnamic acid (0.2mmol,36.5mg mg), bis (p-methylphenyl) phosphine oxide (0.8 mmol,184.2 mg) and rose bengal (0.006mmol, 6.1 mg) were sequentially added, then 1.5mL of DMSO was added, and the reaction tube was placed in a white LED and heated to 40℃and irradiated for 24 hours (the reaction tube was kept at a distance of 8cm from the LED). After the reaction, transferring the reaction solution into a separating funnel, adding 15mL of water, extracting with ethyl acetate (15 mL multiplied by 3 times), merging organic phases, washing with saturated NaCl solution, concentrating the organic phases by using a rotary evaporator to obtain a crude product, and separating by using a thin-layer chromatography preparation plate or a rapid preparation chromatograph (the volume ratio of eluent is ethyl acetate: n-hexane=2:1), thereby obtaining a target product 1- (4-Chlorophenyl) -2- (di-p-tolphosphinyl) ethane-1-one.
1- (4-Chlorophenyl) -2- (di-p-tolylphosphoryl) ethane-1-one was a colorless oil in 75% yield.
1 H NMR(ppm,Chloroform-d)δ7.88(d,2H,J＝8.0Hz),7.57(dd,4H,J＝8.0,12.0Hz),7.32(d,2H,J＝8.0Hz),7.21-7.19(m,4H),4.03(d,2H,J＝16.0Hz),2.32(s,6H).
13 C NMR(ppm,Chloroform-d) 13 C NMR(ppm)δ195.3,173.6,142.9,140.2,135.2,131.2,131.1,130.8,129.5,129.4,128.8,29.7,21.6.
HRMS(ESI)calcd for C 22 H 20 ClNaO 2 P(M+Na) + :405.8135；found:405.8135.
IR(cm -1 )：3012，2983，2821，1745，1583，1453，1371，1338，1039，996，742，626。
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and variations could be made by those skilled in the art without departing from the technical principles of the present invention, and such modifications and variations should also be regarded as being within the scope of the invention.
Claims (8)
1. The synthesis method of the photocatalysis beta-keto diaryl phosphine oxide compound is characterized by comprising the following steps of taking unsaturated carboxylic acid and phosphine oxide hydrogen compound as raw materials, taking visible light as a light source, taking organic dye as a catalyst, and carrying out the following reaction in a solvent DMSO without using other additives:
wherein R is 1 Is Ph, CH 3 Ph、MeOPh、Cl、Br、CF 3 、NO 2 Ph, py or Nap; r is R 2 Is Ph, CH 3 Ph、MeOPh、ClPh、BrPh、CF 3 Ph、NO 2 Ph, py or Nap;
and (3) carrying out post-treatment on the reaction liquid to obtain the beta-ketodiaryl phosphine oxide compound.
2. The method of synthesizing according to claim 1, wherein the source of visible light is a white LED.
3. The method of synthesis according to claim 1, wherein the organic dye is rose bengal or eosin.
4. The synthesis method according to claim 1, wherein the molar ratio of the unsaturated carboxylic acid, the phosphine oxide hydrogen compound and the organic dye is 1:4 (0.01-0.05), the reaction temperature is 25-50 ℃, the continuous stirring is carried out, the light source of visible light is 25-30W, and the reaction time is 24 hours.
5. The method according to claim 1, wherein the post-treatment process comprises transferring the reaction solution into a separating funnel, adding 15mL of water, extracting with ethyl acetate, mixing the organic phases, washing with saturated NaCl solution, concentrating the organic phase with a rotary evaporator to obtain a crude product, and separating to obtain the target product.
6. The method of claim 5, wherein the extraction is performed 3 times with 15mL of ethyl acetate each time.
7. The method of synthesis according to claim 5, wherein separation is performed using a thin layer chromatography preparation plate or a flash preparation chromatograph.
8. The method according to claim 7, wherein the volume ratio of the eluent used in the separation process is ethyl acetate/n-hexane=2:1.
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