CN112142596A - Preparation method of cinnamate compound - Google Patents
Preparation method of cinnamate compound Download PDFInfo
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- CN112142596A CN112142596A CN202011006490.8A CN202011006490A CN112142596A CN 112142596 A CN112142596 A CN 112142596A CN 202011006490 A CN202011006490 A CN 202011006490A CN 112142596 A CN112142596 A CN 112142596A
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- cinnamate
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- -1 cinnamate compound Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229940114081 cinnamate Drugs 0.000 title claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 33
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical class [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000010791 quenching Methods 0.000 claims abstract description 8
- 230000000171 quenching effect Effects 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 7
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 7
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- ZBIKORITPGTTGI-UHFFFAOYSA-N [acetyloxy(phenyl)-$l^{3}-iodanyl] acetate Chemical compound CC(=O)OI(OC(C)=O)C1=CC=CC=C1 ZBIKORITPGTTGI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 2
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- DDTLUYCURNSZFH-UHFFFAOYSA-N n'-(2,4,6-trimethylphenyl)ethane-1,2-diamine Chemical compound CC1=CC(C)=C(NCCN)C(C)=C1 DDTLUYCURNSZFH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 238000004440 column chromatography Methods 0.000 abstract description 6
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- 150000002940 palladium Chemical class 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid Chemical class OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- KBEBGUQPQBELIU-CMDGGOBGSA-N Ethyl cinnamate Chemical compound CCOC(=O)\C=C\C1=CC=CC=C1 KBEBGUQPQBELIU-CMDGGOBGSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000001503 aryl iodides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FWNJUSYYKZFUQB-UHFFFAOYSA-M bis(4-chlorophenyl)iodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(Cl)=CC=C1[I+]C1=CC=C(Cl)C=C1 FWNJUSYYKZFUQB-UHFFFAOYSA-M 0.000 description 1
- UVESIIOEMWGOPI-UHFFFAOYSA-M bis(4-methoxyphenyl)iodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(OC)=CC=C1[I+]C1=CC=C(OC)C=C1 UVESIIOEMWGOPI-UHFFFAOYSA-M 0.000 description 1
- 239000001405 butyl (E)-3-phenylprop-2-enoate Substances 0.000 description 1
- OHHIVLJVBNCSHV-KTKRTIGZSA-N butyl cinnamate Chemical compound CCCCOC(=O)\C=C/C1=CC=CC=C1 OHHIVLJVBNCSHV-KTKRTIGZSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- KBEBGUQPQBELIU-UHFFFAOYSA-N cinnamic acid ethyl ester Natural products CCOC(=O)C=CC1=CC=CC=C1 KBEBGUQPQBELIU-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- NBFNGRDFKUJVIN-VAWYXSNFSA-N phenyl (e)-3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1/C=C/C(=O)OC1=CC=CC=C1 NBFNGRDFKUJVIN-VAWYXSNFSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of cinnamate compounds, which comprises the steps of sequentially adding diaryl trifluoromethanesulfonic acid iodine compounds, acrylate compounds, palladium complexes, additives and solvents into a reaction bottle for reaction, and stirring at 70-90 ℃ for 15-20 hours; then quenching and extracting are carried out; drying the extract, filtering, concentrating, and purifying by column chromatography to obtain cinnamate compounds. The method effectively solves the problems of large consumption and overhigh reaction temperature of the traditional reaction catalyst, provides a method which can give full play to the performance of the palladium catalyst, ensures that the palladium catalyst can rapidly implement the coordination reaction of electron-poor olefin, improves the service efficiency of the catalyst, reduces the reaction temperature, does not need special reaction environment, has simple and easily obtained raw materials and loose reaction conditions, and is a low-cost preparation method of the cinnamate compounds.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of cinnamate compounds
Background
Cinnamates have been favored by researchers in the fields of fine chemicals and daily chemicals as important organic raw material intermediates for medicines, organisms, perfumes, and dyes.
The traditional method for obtaining the cinnamate compounds is that aryl iodide and acrylates are subjected to Heck coupling reaction under the combined action of a transition metal palladium catalyst, an organic phosphine ligand and alkali; the activity of the palladium catalyst determines the quality of the overall reaction, wherein the electronic effect of the aromatic hydrocarbon substituent and the electron density of the olefin pi bond have great influence on the reaction, and if poor electron olefin is encountered, the palladium catalyst with low activity is difficult to perform a coordination reaction with the poor electron olefin to influence the efficiency of the overall reaction.
However, in the actual operation process, the phosphine ligand is easily oxidized, and the surface of the carrier is not firmly connected with palladium by chemical bonds, so that the loss of palladium in circulation is large, the catalytic activity of the catalyst is quickly reduced along with the increase of the circulation times, so that the palladium catalyst is inactivated, more palladium needs to be added into the reaction, the heavy metal palladium is polluted and wasted, and the palladium metal is expensive, so that the traditional manufacturing method is high in cost and is not suitable for large-scale production. Therefore, how to reduce the consumption of palladium catalyst and maintain its high activity is a problem to be solved urgently in the industry.
Disclosure of Invention
The purpose of the application is to provide a preparation method of cinnamate compounds, which can give full play to the performance of a palladium catalyst, lead the palladium catalyst to be capable of quickly carrying out a coordination reaction on electron-poor olefins, improve the service efficiency of the catalyst, reduce the reaction temperature, avoid the need of special reaction environment, and have the advantages of simple and easily obtained raw materials, loose reaction conditions and low cost.
In order to solve the above technical problem, the following technical solutions are adopted in the present application:
a preparation method of cinnamate compounds is characterized by comprising the following steps: adding diaryl trifluoromethanesulfonic acid iodine compound, acrylate compound, palladium complex, additive and solvent into a reaction container to form a mixture; the adding molar ratio of the diaryl trifluoromethanesulfonic acid iodine compound to the acrylate compound is 1:1.5-1: 2.0; the addition molar ratio of the addition amount of the palladium complex compound to the addition of the diaryl trifluoromethanesulfonic acid iodine compound is 0.02:1-0.06: 1;
reacting the mixture at 70-90 ℃ for 15-20 hours, then quenching and extracting the obtained reactant, drying the obtained extract, filtering, concentrating and purifying to obtain the product.
Further, the structural formula of the palladium complex is shown as formula I:
further, the preparation method of the palladium complex is characterized by comprising the following steps:
(1): adding N-N' -di (2,4, 6-trimethyl) phenyl ethylenediamine, palladium chloride and dehydrated tetrahydrofuran into a reaction vessel for reaction;
(2): heating the reaction system to 55 ℃ and stirring for 18 hours under the protection of nitrogen;
(3): the solvent is removed by concentration under vacuum, and then the palladium complex is obtained by recrystallization by using a mixed solvent of dichloromethane and petroleum ether.
Further, the additive is one of copper acetate monohydrate, copper chloride dihydrate, silver carbonate, potassium persulfate and iodobenzene diacetate.
Further, the solvent is one of toluene, dichloroethane, acetonitrile, ethanol and dioxane.
Further, the cinnamic acid ester compound has a general formula shown in formula II:
wherein R1 is one of a hydrogen atom, an electron donating group, an electron withdrawing group, and a halogen; r2 is one of alkyl, cycloalkyl, phenyl and benzyl.
Further, the electron-donating group is one of methyl, ethyl, tert-butyl, methoxy and ethoxy; the electron-withdrawing group is one of nitro and ester group; the halogen is one of fluorine, chlorine and bromine.
The application successfully carries out coupling reaction with diaryl trifluoromethanesulfonic acid iodides and acrylate compounds by using a palladium complex to produce cinnamate compounds. The optimized palladium complex is used as a catalyst of the whole reaction, the palladium complex is provided with a bidentate amine ligand, the catalyst can replace a zero-valent palladium catalyst to provide enough electron density to coordinate with a poor electron group, the whole coupling reaction is further activated, a phosphorus ligand and a pure oxygen reaction environment do not need to be additionally added, the process steps are saved, the activity of the whole reaction is ensured, the using amount of the catalyst is reduced, the reaction temperature is reduced, the catalyst can be rapidly paired with the poor electron group, the reaction speed is improved, and the cost is saved. The method has the characteristics of mild reaction conditions, convenient operation, simple synthesis process, low catalyst consumption, suitability for industrial production and the like.
Drawings
The invention has no attached figure
Detailed Description
The invention is described in more detail below by way of examples, it being necessary to point out here: this example is provided for further illustration of the invention and is not intended to limit its scope. Various modifications of the invention which do not depart from the spirit of the invention will become apparent to those skilled in the art from the invention and fall within the scope of the invention as claimed.
Example 1:
to the reaction flask were added 0.3 mmol of iodine diphenyltrifluoromethanesulfonate, 0.45 mmol of ethyl acrylate, 0.006 mmol of palladium complex, 0.3 mmol of silver carbonate and 1.5 ml of dichloroethane in this order, and the reaction was stirred sufficiently at 80 ℃ for 15 hours using an electric stirrer. After the reaction is finished, saturated saline solution is used for quenching, ethyl acetate is used for extraction for three times, extract liquor is dried by anhydrous sodium sulfate, filtered and concentrated, and column chromatography purification is carried out to obtain ethyl cinnamate, wherein the yield is 80%. Nuclear magnetic resonance spectroscopy: 1H NMR (400MHz, CDCl3):7.69(d, J ═ 16.0Hz, 1H), 7.54-7.52(m, 2H), 7.39-7.38(m, 3H), 6.44(d, J ═ 16.0Hz, 1H), 4.27(q, J ═ 3.2Hz, 2H), 1.34(t, J ═ 7.2Hz, 3H); 13C NMR (100MHz, CDCl3) 167.0, 144.6, 134.5, 130.2, 128.9, 128.0, 118.3, 60.5, 14.3.
Example 2:
to the reaction flask were added 0.3 mmol of iodine diphenyltrifluoromethanesulfonate, 0.45 mmol of butyl acrylate, 0.009 mmol of palladium complex, 0.3 mmol of silver carbonate and 2.0 ml of dichloroethane in this order, and the reaction was stirred well at 80 ℃ for 18 hours using an electric stirrer. After the reaction is finished, saturated saline solution is used for quenching, ethyl acetate is used for extracting for three times, the extract liquid is dried by anhydrous sodium sulfate, filtered and concentrated, and column chromatography purification is carried out to obtain the butyl cinnamate, wherein the yield is 82%. Nuclear magnetic resonance spectroscopy: 1H NMR (400MHz, CDCl3):7.68(d, J ═ 16.0Hz, 1H), 7.53-7.51(m, 2H), 7.38-7.37(m, 3H), 6.44(d, J ═ 16.0Hz, 1H), 4.21(t, J ═ 6.8Hz, 2H), 1.73-1.66(m, 2H), 1.49-1.39(m, 2H), 0.97(t, J ═ 7.4Hz, 3H); 13C NMR (100MHz, CDCl3) 167.0, 144.5, 134.4, 130.1, 128.8, 128.0, 118.2, 64.4, 30.7, 19.1, 13.7.
Example 3:
to the reaction flask were added 0.3 mmol of iodine diphenyltrifluoromethanesulfonate, 0.45 mmol of phenyl acrylate, 0.009 mmol of palladium complex, 0.3 mmol of silver carbonate and 2.0 ml of dichloroethane in this order, and the reaction was stirred sufficiently at 90 ℃ for 20 hours using an electric stirrer. After the reaction is finished, saturated saline solution is used for quenching, ethyl acetate is used for extracting for three times, extract liquor is dried by anhydrous sodium sulfate, filtered and concentrated, and column chromatography purification is carried out to obtain the phenyl cinnamate, wherein the yield is 73%. Nuclear magnetic resonance spectroscopy: 1H NMR (400MHz, CDCl3):7.91(d, J ═ 16.0Hz, 1H), 7.64-7.62(m, 2H), 7.47-7.43(m, 5H), 7.29(t, J ═ 7.6Hz, 1H), 7.21(d, J ═ 7.6Hz, 2H), 6.68(d, J ═ 16.0Hz, 1H); 13C NMR (100MHz, CDCl3) 165.4, 150.8, 146.5, 134.1, 130.7, 129.4, 129.0, 128.3, 125.8, 121.6, 117.3.
Example 4:
to a reaction flask were added 0.3 mmol of bis (4-methoxyphenyl) iodonium trifluoromethanesulfonate, 0.45 mmol of butyl acrylate, 0.006 mmol of palladium complex, 0.3 mmol of silver carbonate and 1.5 ml of dichloroethane in this order, and the reaction was stirred sufficiently at 70 ℃ for 15 hours using an electric stirrer. After the reaction is finished, quenching the mixture by using saturated saline solution, extracting the mixture for three times by using ethyl acetate, drying the extract by using anhydrous sodium sulfate, filtering and concentrating the extract, and purifying the extract by using column chromatography to obtain the 3- (4-methoxyphenyl) butyl acrylate with the yield of 82 percent. Nuclear magnetic resonance spectroscopy: 1H NMR (400MHz, CDCl3):7.64(d, J ═ 16.0Hz, 1H), 7.48(d, J ═ 8.4Hz, 2H), 6.90(d, J ═ 8.8Hz, 2H), 6.31(d, J ═ 16.0Hz, 1H), 4.20(t, J ═ 6.6Hz, 2H), 3.84(s, 3H), 1.72-1.65(m, 2H), 1.48-1.39(m, 2H), 0.96(t, J ═ 7.4Hz, 3H); 13C NMR (100MHz, CDCl3) 167.4, 161.3, 144.2, 129.7, 127.2, 115.8, 114.3, 64.3, 55.4, 30.8, 19.2, 13.7.
Example 5: to a reaction flask were added 0.3 mmol of bis (4-chlorophenyl) iodonium trifluoromethanesulfonate, 0.45 mmol of butyl acrylate, 0.006 mmol of palladium complex, 0.3 mmol of silver carbonate and 1.5 ml of dichloroethane in this order, and the reaction was stirred well at 80 ℃ for 20 hours using an electric stirrer. After the reaction is finished, quenching the mixture by using saturated saline solution, extracting the mixture for three times by using ethyl acetate, drying the extract by using anhydrous sodium sulfate, filtering and concentrating the extract, and purifying the extract by using column chromatography to obtain the 3- (4-chlorphenyl) butyl acrylate with the yield of 70 percent. Nuclear magnetic resonance spectroscopy: 1H NMR (400MHz, CDCl3):7.62(d, J ═ 16.0Hz, 1H), 7.46(d, J ═ 8.8Hz, 2H), 7.35(t, J ═ 8.4Hz, 2H), 6.41(d, J ═ 16.0Hz, 1H), 4.21(t, J ═ 6.6Hz, 2H), 1.72-1.65(m, 2H), 1.48-1.39(m, 2H), 0.96(t, J ═ 7.4Hz, 3H); 13C NMR (100MHz, CDCl3) 166.8, 143.1, 136.1, 133.0, 129.2, 129.1, 118.9, 64.5, 30.7, 19.2, 13.7.
The above embodiments 1 to 5 are only a few common examples of the present invention, and do not limit the present invention in other forms.
Claims (7)
1. A preparation method of cinnamate compounds is characterized by comprising the following steps:
adding diaryl trifluoromethanesulfonic acid iodine compound, acrylate compound, palladium complex, additive and solvent into a container to form a mixture;
the adding molar ratio of the diaryl trifluoromethanesulfonic acid iodine compound to the acrylate compound is 1:1.5-1: 2.0; the addition molar ratio of the addition amount of the palladium complex compound to the addition of the diaryl trifluoromethanesulfonic acid iodine compound is 0.02:1-0.06: 1;
reacting the mixture at 70-90 ℃ for 15-20 hours, then quenching and extracting the obtained reactant, drying the obtained extract, filtering, concentrating and purifying to obtain the product.
2. The method for preparing cinnamate compounds according to claim 1, wherein the palladium complex has a structural formula represented by formula i:
3. the method for preparing a palladium complex compound according to claim 2, comprising the steps of:
(1): adding N-N' -di (2,4, 6-trimethyl) phenyl ethylenediamine, palladium chloride and dehydrated tetrahydrofuran into a reaction vessel for reaction;
(2): heating the reaction system to 55 ℃ and stirring for 18 hours under the protection of nitrogen;
(3): the solvent is removed by concentration under vacuum, and then the palladium complex is obtained by recrystallization by using a mixed solvent of dichloromethane and petroleum ether.
4. The method for preparing cinnamate compounds according to claim 1, wherein the additive is one of copper acetate monohydrate, copper chloride dihydrate, silver carbonate, potassium persulfate, and iodobenzene diacetate.
5. The method for preparing cinnamate compounds according to claim 1, wherein the solvent is one of toluene, dichloroethane, acetonitrile, ethanol, and dioxane.
6. The cinnamate compound of formula ii prepared by the process of any one of claims 1 to 5, wherein the cinnamate compound has a general formula of formula ii:
wherein R is1Is one of hydrogen atom, electron-donating group, electron-withdrawing group and halogen; r2Is one of alkyl, cycloalkyl, phenyl and benzyl.
7. The cinnamate compound according to claim 6, wherein the electron donating group is one of methyl, ethyl, tert-butyl, methoxy, and ethoxy; the electron-withdrawing group is one of nitro and ester group; the halogen is one of fluorine, chlorine and bromine.
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Non-Patent Citations (4)
| Title |
|---|
| GUIYAN LIU ECT.: ""A Highly Active Catalyst System for Suzuki–Miyaura Coupling of Aryl Chlorides"", 《ORGANOMETALLICS》 * |
| LI, JIAN ET AL.: ""Palladium-catalyzed heck-type arylation of acrylate with diaryliodonium salts"", 《RSC ADVANCES》 * |
| PEREZ, JUANA M.ET AL.: "Palladium(II) oxide impregnated on magnetite as a catalyst for the synthesis of 4-arylcoumarins via a Heck-arylation/cyclization process", 《RSC ADVANCES》 * |
| SHI-MENG WANG ECT.: ""Palladium-catalyzed Mizoroki–Heck-type reactions of [Ph2SRfn][OTf] with alkenes at room temperature"", 《CHEMICAL COMMUNICATIONS》 * |
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