CN109896944B - Method for synthesizing 1, 4-naphthoquinone cyclopropane compound - Google Patents
Method for synthesizing 1, 4-naphthoquinone cyclopropane compound Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 27
- -1 1, 4-naphthoquinone cyclopropane compound Chemical class 0.000 title claims abstract description 25
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 18
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 17
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 10
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000005513 chalcones Nutrition 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 51
- 239000002904 solvent Substances 0.000 claims description 41
- 238000004440 column chromatography Methods 0.000 claims description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000741 silica gel Substances 0.000 claims description 21
- 229910002027 silica gel Inorganic materials 0.000 claims description 21
- 239000003480 eluent Substances 0.000 claims description 19
- 238000004821 distillation Methods 0.000 claims description 17
- 239000003208 petroleum Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 6
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 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 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 claims description 2
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 claims description 2
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 2
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 claims description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000001704 evaporation Methods 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
- 238000000746 purification Methods 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 60
- 239000000047 product Substances 0.000 description 16
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- 238000012512 characterization method Methods 0.000 description 15
- 238000001816 cooling Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 12
- 229930192627 Naphthoquinone Natural products 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 150000002791 naphthoquinones Chemical class 0.000 description 5
- 230000004071 biological effect Effects 0.000 description 4
- 238000005888 cyclopropanation reaction Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 3
- 150000000191 1,4-naphthoquinones Chemical class 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001942 cyclopropanes Chemical class 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- KQPYUDDGWXQXHS-UHFFFAOYSA-N juglone Chemical compound O=C1C=CC(=O)C2=C1C=CC=C2O KQPYUDDGWXQXHS-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CICPINMHVINFBQ-GHRIWEEISA-N (E)-1-[5-methoxy-2-(2-phenylethynyl)phenyl]-3-phenylprop-2-en-1-one Chemical compound COC1=CC(=C(C=C1)C#CC2=CC=CC=C2)C(=O)/C=C/C3=CC=CC=C3 CICPINMHVINFBQ-GHRIWEEISA-N 0.000 description 1
- XJXYCSAXFPPYNQ-WUKNDPDISA-N (E)-3-(2-fluorophenyl)-1-[2-(2-phenylethynyl)phenyl]prop-2-en-1-one Chemical compound C1=CC=C(C=C1)C#CC2=CC=CC=C2C(=O)/C=C/C3=CC=CC=C3F XJXYCSAXFPPYNQ-WUKNDPDISA-N 0.000 description 1
- BYJITRACHDOYQT-ISLYRVAYSA-N (E)-3-(2-methylphenyl)-1-[2-(2-phenylethynyl)phenyl]prop-2-en-1-one Chemical compound CC1=CC=CC=C1/C=C/C(=O)C2=CC=CC=C2C#CC3=CC=CC=C3 BYJITRACHDOYQT-ISLYRVAYSA-N 0.000 description 1
- LMQIMJAOKKKLNU-GHRIWEEISA-N (E)-3-(4-bromophenyl)-1-[2-(2-phenylethynyl)phenyl]prop-2-en-1-one Chemical compound C1=CC=C(C=C1)C#CC2=CC=CC=C2C(=O)/C=C/C3=CC=C(C=C3)Br LMQIMJAOKKKLNU-GHRIWEEISA-N 0.000 description 1
- MMZYNEPZPQATAS-FBMGVBCBSA-N (E)-3-(4-methylphenyl)-1-[2-(2-phenylethynyl)phenyl]prop-2-en-1-one Chemical compound Cc1ccc(\C=C\C(=O)c2ccccc2C#Cc2ccccc2)cc1 MMZYNEPZPQATAS-FBMGVBCBSA-N 0.000 description 1
- ZDFMJWBDVMKSGL-SAPNQHFASA-N (E)-3-(4-methylphenyl)-1-[4-methyl-2-(2-phenylethynyl)phenyl]prop-2-en-1-one Chemical compound CC1=CC=C(C=C1)/C=C/C(=O)C2=C(C=C(C=C2)C)C#CC3=CC=CC=C3 ZDFMJWBDVMKSGL-SAPNQHFASA-N 0.000 description 1
- KWRGDBCCUVFYND-FBMGVBCBSA-N (E)-3-phenyl-1-[2-(2-phenylethynyl)phenyl]prop-2-en-1-one Chemical compound O=C(\C=C\c1ccccc1)c1ccccc1C#Cc1ccccc1 KWRGDBCCUVFYND-FBMGVBCBSA-N 0.000 description 1
- GTNBAEQCWCKMSU-GHRIWEEISA-N (E)-3-phenyl-1-[2-[2-[4-(trifluoromethyl)phenyl]ethynyl]phenyl]prop-2-en-1-one Chemical compound C1=CC=C(C=C1)/C=C/C(=O)C2=CC=CC=C2C#CC3=CC=C(C=C3)C(F)(F)F GTNBAEQCWCKMSU-GHRIWEEISA-N 0.000 description 1
- OTBHDFWQZHPNPU-UHFFFAOYSA-N 1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CCCC2 OTBHDFWQZHPNPU-UHFFFAOYSA-N 0.000 description 1
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- PDAQFIFHJIRWEX-UHFFFAOYSA-N 2,3-dihydroanthracene-1,4-dione Chemical class C1=CC=C2C=C3C(=O)CCC(=O)C3=CC2=C1 PDAQFIFHJIRWEX-UHFFFAOYSA-N 0.000 description 1
- 150000004550 2-hydroxy-1,4-naphthoquinones Chemical class 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 238000006419 Freund reaction Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010067197 Tinea manuum Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000000078 anti-malarial effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 1
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- 229930014626 natural product Natural products 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
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- 238000007243 oxidative cyclization reaction Methods 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for synthesizing 1, 4-naphthoquinone cyclopropane and derivatives thereof. The synthesis method comprises the steps of taking an o-alkynyl chalcone compound shown in a formula (I) as an initiator, taking ferric chloride or ferric nitrate as a catalyst, reacting for 0.1-1h in an organic solvent at the temperature of 80-120 ℃ under the condition that diiodo pentoxide is taken as an oxidant, and separating and purifying to obtain a corresponding target product. The synthesis method has the characteristics of small harm to the environment, mild reaction conditions, simple and convenient operation and the like.
Description
Technical Field
The invention relates to a synthesis method of an organic compound, in particular to a preparation method for synthesizing a 1, 4-naphthoquinone cyclopropane compound.
Background
1, 4-naphthoquinone has wide application in the aspects of dyes, organic medical intermediates and the like due to the unique properties of the naphthoquinone, and becomes a hot spot. In industrial production, 1, 4-naphthoquinone is an important raw material in fine chemical engineering, is widely applied to intermediates of dyes, medicines, perfumes, pesticides, plasticizers and the like, is a polymerization regulator for synthesizing rubber and resin, and is an important substance for synthesizing novel papermaking cooking aids, for example, 1, 4-naphthoquinone is an important intermediate for synthesizing naphthoquinone dyes and derivatives thereof, anthraquinone, tetrahydroanthraquinone, high-purity 1-aminoanthraquinone and antitumor drugs, is a raw material for synthesizing 2, 3-dihydro-1, 4-anthraquinone series dyes, and can be used as a polymerization regulator, a curing agent for photochemical cross-linked polyester, a corrosion inhibitor, a stabilizer for transformer oil, synthetic flame-retardant polyester and the like. Meanwhile, 1, 4-naphthoquinone compounds are small molecular compounds widely existing in nature and have various biological activities, for example, many derivatives of 1, 4-naphthoquinone have good bactericidal, medical and biological properties, such as antimalarial activity, and researches show that 5-hydroxy-1, 4-naphthoquinone has hemostatic and antibacterial activities and is used for treating eczema, tinea manuum and tinea pedis; the derivative of 2-hydroxy-1, 4-naphthoquinone is effective inhibitor for tumor cell respiration, and its bridged complex has wide application. Due to the wide application range, the method for efficiently and environmentally synthesizing the 1, 4-naphthoquinone is very important to find. The synthesis of naphthoquinone has been reported at home and abroad, for example, chromium trioxide is used as an oxidant to oxidize polycyclic aromatic hydrocarbon containing side chains under an acidic condition, but the method has a complex process, high cost for producing 1, 4-naphthoquinone and certain limitation; furthermore, a liquid phase oxidation method of naphthalene is adopted, high-valence heavy metal salt is used for indirect electrolytic oxidation, and HNO is used3，H2O2，IO4 -，S2O4 2-The method for preparing naphthoquinone by oxidizing nonmetal oxides has the disadvantages of high energy consumption, difficult naphthoquinone separation, more reaction byproducts and great pollution.
In addition, cyclopropane structures are widely present in natural products and drug molecules and have good biological activity. For example, the sponge extract (1) has an antitumor activity, the pyrethroid (2) has an insecticidal activity, and the like. Meanwhile, cyclopropane structures belong to the smallest cyclic structures, and the backbone thereof has a rigid planar structure and a specific bond angle, and can construct a plurality of chiral centers, and thus have recently been receiving attention from chemists.
The cyclopropane compound not only has various biological activities, but also is a key intermediate for synthesizing a plurality of pesticides and drug molecules, so the research on the synthesis method of the cyclopropane compound has important significance and is a hotspot in the field of organic chemistry. There are also many conventional methods for synthesizing cyclopropane compounds, for example, Freund's reaction (3), ylide cyclopropanation (4), carbene cyclopropanation (5), and the like. However, the traditional synthesis method has a lot of disadvantages, equivalent metallic sodium is needed in the Freund reaction, and the operation process has certain dangerousness; the ylide cyclopropanation reaction can generate a large amount of waste, and the atom utilization rate is very low; the carbene cyclopropanation reaction synthesizes cyclopropane compounds through the [2+1] cyclization reaction of olefin and active intermediate carbene, and the method also has the defect of low atom utilization rate.
Aiming at the defects of the traditional cyclopropane compound synthesis, the recent Kazuhiko Takai and the like utilize olefin and I2CHB(OR)2Synthesis of borocyclopropane compounds under the catalysis of chromium chloride [ see org. Lett.,2017,19(22), pp 6104-6107-]However, the method needs to add 6 times of equivalent of chromium dichloride, and a large amount of metal waste is generated after the reaction, which is not beneficial to industrial production.
Compared with the traditional synthesis method for synthesizing the 1, 4-naphthoquinone and the cyclopropane compound, the synthesis method disclosed by the patent has great advantages, the method related to the patent can be used for synthesizing the 1, 4-naphthoquinone cyclopropane compound in one step by adopting a one-pot method under mild conditions, the steps are simple, the efficiency is higher, and the method has a greater prospect in the aspect of industrial application.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a general, simple and efficient method for synthesizing 1, 4-naphthoquinocyclopropane compounds and derivatives thereof.
The technical scheme of the invention is as follows:
a method for synthesizing 1, 4-naphthoquinocyclopropane compounds comprises the following steps: taking an o-alkynyl chalcone compound shown in a formula (I) as an initiator, reacting at the temperature of 80-100 ℃ in the presence of a catalyst, an oxidant and a solvent, and separating and purifying to obtain a 1, 4-naphthoquinone cyclopropane compound shown in a formula (II); the catalyst is ferric trichloride or ferric nitrate;
in formula (I) or formula (II), R1Is phenyl, 2-fluorophenyl, 3-chlorophenyl, 4-bromophenyl, 2-methylbenzene, 4-methylphenyl, 2-methoxyphenyl or 4-cyanophenyl, thienyl, R2Is H, methyl or methoxy, R3Is phenyl, 4-propylphenyl, 2-fluorophenyl or 4-trifluoromethylphenyl;
the reaction formula is as follows:
in the reaction, the catalyst is ferric chloride or ferric nitrate, and the amount of the catalyst substance is 5-30 percent, most preferably 20 percent of the amount of the o-alkynyl chalcone compound substance shown in the formula (I).
In the reaction of the invention, the oxidant is one or two of diiodo pentaoxide and iodobenzene diacetate.
Further, the amount of the oxidant is 100-400%, most preferably 300% of the amount of the ortho-alkynyl chalcone compound represented by the formula (I).
In the reaction of the invention, the solvent is one or more of acetonitrile, dichloromethane, toluene, 1, 4-dioxane and the like, and the optimal solvent is 1, 4-dioxane.
Furthermore, the volume of the solvent is 5-10 mL/mmol based on the substance of the ortho-alkynyl chalcone compound shown in the formula (I).
The reaction temperature of the reaction is 80-120 ℃, and the optimal reaction temperature is 100 ℃.
The reaction time of the reaction is 0.1-1.0h, and the optimal reaction time is 0.5 h.
The separation and purification of the invention are as follows: adding column chromatography silica gel into the reaction liquid, removing the solvent through reduced pressure distillation, separating through column chromatography, eluting by using a mixed solution of petroleum ether and ethyl acetate with the volume ratio of 20:1 as an eluent, collecting the eluent containing the target product, and evaporating the solvent to obtain the 1, 4-naphthoquinone cyclopropane compound shown in the formula (II).
Furthermore, the column chromatography silica gel is 100-200 meshes. Furthermore, the mass of the column chromatography silica gel is 0.5 g.
Preferably, the 1, 4-naphthoquinocyclopropane compound represented by the formula (II) of the present invention is one of the following compounds:
compared with the prior art, the invention has the beneficial effects that:
(1) the method is safe and environment-friendly, does not generate waste gas, and has low operation risk;
(2) the substrate has good adaptability, and various substituents can realize oxidative cyclization;
(3) the reaction condition is mild;
(4) meanwhile, the reaction has certain innovation, and the 1, 4-naphthoquinone cyclopropane compound can be directly synthesized in one step.
Detailed Description
The invention will be further illustrated by the following examples, without limiting the scope of the invention:
example 1
0.3mmol (E) -3-phenyl-1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.06mmol ferric chloride, 0.9mmol diiodo pentoxide were added to a 15mL thick-walled pressure-resistant reaction tube, and 3mL 1, 4-dioxane was added as a solvent. Then, the mixture was magnetically stirred at 100 ℃ for 0.5 hour. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (petroleum ether/ethyl acetate ═ 20:1 as eluent). The material was a white solid in 68% yield.
Characterization data:1H NMR(500MHz,CDCl3)：δ8.21-8.18(m，1H),8.15,-8.12(m，1H),7.84-7.80(m，2H),7.27-7.24(m，3H),7.17-7.09(m，5H),6.78(d,J＝7Hz,2H),3.69(d,J＝6Hz,1H),3.45(d,J＝6Hz,1H)
13C NMR(125MHz,CDCl3):δ192.73,191.06,134.48,134.24,133.36,132.52,132.50,131.87,131.64,128.68,128.50,128.08,128.03,127.55,127.02,126.81,77.29,77.03,76.78,50.87,43.07,39.92
example 2
0.3mmol (E) -1- (2- (phenylethynyl) phenyl) -3- (o-tolyl) prop-2-en-1-one, 0.06mmol ferric nitrate, and 0.9mmol diiodo pentoxide were put into a 15mL thick-walled pressure-resistant reaction tube, and 3mL 1, 4-dioxane was added as a solvent. Then, the mixture was magnetically stirred at 100 ℃ for 0.5 hour. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (petroleum ether/ethyl acetate ═ 20:1 as eluent). The material was a white solid in 51% yield.
Characterization data:1H NMR(500MHz,CDCl3):δ8.25-8.20(m，1H)8.17-8.12(m，1H),7.84-7.79(m，2H),7.22-7.17(m，3H),7.15-7.11(m,3H),7.06-7.03(m,1H),6.86(t,J＝8Hz,1H),6.54(d，J＝8Hz，1H),3.87(d，J＝8Hz，1H),3.50(d，J＝8Hz，1Hz),2.40(s，3H).
13C NMR(125MHz,CDCl3)δ192.97,191.38,137.37,134.51,134.23,132.57,132.46,131.88,131.23,130.06,127.99,127.94,127.85,127.56,126.83,125.77,125.76,49.86,41.31,38.02,19.90.
example 3
0.3mmol of (E) -3- (2-methoxyphenyl) -1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.03mmol of ferric chloride and 0.9mmol of diiodo pentoxide were put into a 15mL thick-walled pressure-resistant reaction tube, and 3mL of 1, 4-dioxane was added as a solvent. Then, the mixture was magnetically stirred at 100 ℃ for 0.5 hour. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (petroleum ether/ethyl acetate ═ 20:1 as eluent). The material was a white solid in 78% yield.
Characterization data:1H NMR(500MHz,CDCl3)：δ8.23-8.19(m，1H),8.14-8.10(m，1H),7.81-7.77(m，2H),7.22-7.17(m，5H),7.13-7.10(m，1H),6.80(d，J＝8Hz，1H),6.61(t，J＝8Hz，1H),6.52(dd，J1＝7.5Hz，J2＝1Hz，1H)3.82(s，3H),3.77-3.74(m，2H).13C NMR(125MHz,CDCl3)δ193.31,191.62,158.21,134.31,133.96,132.76,132.60,132.24,131.29,128.73,128.00,127.84,127.75,127.14,126.64,121.73,119.98,109.92,55.34,49.79,38.52,38.03.
example 4
0.3mmol of (E) -1- (2- (phenylethynyl) phenyl) -3- (thien-2-yl) prop-2-en-1-one, 0.09mmol of ferric chloride and 0.9mmol of diiodo pentoxide were put into a 15mL thick-walled pressure-resistant reaction tube, and 3mL of 1, 4-dioxane was added as a solvent. Then, the mixture was magnetically stirred at 100 ℃ for 0.5 hour. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (petroleum ether/ethyl acetate ═ 20:1 as eluent). The material was a white solid in 64% yield.
Characterization data:1H NMR(500MHz,CDCl3):δ8.20-8.16(m，1H),8.14-8.11(m，1H)，7.83-7.79(m，2H),7.33-7.27(m，5H),7.04(dd，J1＝5Hz，J2＝1Hz，1H),6.76(dd，J1＝5Hz，J2＝3.5Hz，1H),6.52(d，J＝3Hz，1H),3.64(d,J＝5.5Hz，1H),3.58(d，J＝5.5Hz，1H)
13C NMR(125MHz,CDCl3)：δ191.88,190.47,137.03,134.54,134.32,132.43,132.36,131.81,131.62,128.27,128.10,126.85,126.73,126.53,125.29,50.92,42.02,38.44,1.01.
example 5
0.3mmol of (E) -3- (3-chlorophenyl) -1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.06mmol of ferric chloride and 0.9mmol of iodobenzene diacetate were placed in a 15mL thick-walled pressure-resistant reaction tube, and 3mL of 1, 4-dioxane was added as a solvent. Then, the mixture was magnetically stirred at 100 ℃ for 0.5 hour. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (petroleum ether/ethyl acetate ═ 20:1 as eluent). The material was a white solid in 56% yield.
Characterization data:1H NMR(500MHz,CDCl3)：δ8.19-8.15(m，1H),8.14-8.10(m，1H),7.82,-7.78(m，2H),7.30-7.27(m，3H),7.18-7.16(m，2H),7.12-7.09(m，1H),7.01(t，J＝8Hz，1H),6.84(t，J＝2Hz,1H),6.58(d，J＝8Hz，1H),3.65(d，J＝5.5Hz，1H),3.39(d，J＝5.5Hz，1H).
13C NMR(126MHz,CDCl3)δ192.21,190.62,135.54,134.55,134.30,133.99,132.35,132.33,131.77,131.16,129.19,128.44,128.24,128.20,128.11,127.66,126.81,125.85,77.28,77.03,76.78,50.58,42.01,39.71.
example 6
0.3mmol of (E) -3- (4-bromophenyl) -1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.06mmol of ferric chloride and 0.3mmol of diiodo pentoxide were put into a 15mL thick-walled pressure-resistant reaction tube, and 3mL of 1, 4-dioxane was added as a solvent. Then, the mixture was magnetically stirred at 100 ℃ for 0.5 hour. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (petroleum ether/ethyl acetate ═ 20:1 as eluent). The material was a white solid in 52% yield.
Characterization data:1H NMR(500MHz,CDCl3)：δ8.19-8.15(m,1H),8.13-8.10(m，1H),7.82-7.79(m，2H),7.30-7.27(m，3H),7.23-7.21(m，2H),7.16-7.14(m，2H),6.64-6.61(m，2H),3.62(d，J＝5.5Hz，1H),3.38(d，J＝5.5Hz，1H).
13C NMR(125MHz,CDCl3)：δ192.27,190.65,134.52,134.27,132.57,132.34,132.31,131.77,131.22,131.17,129.53,128.07,126.79,121.57,50.60,42.12,39.86.
example 7
0.3mmol of (E) -1- (2- (phenylethynyl) phenyl) -3- (p-tolyl) prop-2-en-1-one, 0.06mmol of ferric chloride and 0.9mmol of diiodo pentoxide were put into a 15mL thick-walled pressure-resistant reaction tube, and 3mL of acetonitrile was added as a solvent. Then, the mixture was magnetically stirred at 100 ℃ for 0.5 hour. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (petroleum ether/ethyl acetate ═ 20:1 as eluent). The material was a white solid in 62% yield.
Characterization data:1H NMR(500MHz,CDCl3)：δ8.24-8.21(m，1H),8.16-8.13(m，1H),7.84-7.79(m，2H),7.21-7.18(m，3H),7.15-7.11(m，3H),7.06-7.03(m，1H),6.86(t，J＝7.5Hz，1H),6.54(d，J＝7.5Hz，1H),3.87(d，J＝6Hz，1H),3.50(d，J＝6Hz，1H),2.40(s，3H)13C NMR(125MHz,CDCl3)：δ192.96,191.37,137.36,134.50,134.22,132.56,132.45,131.87,131.22,130.05,127.98,127.94,127.84,127.55,126.82,125.75,49.85,41.30,38.00,19.89.
example 8
0.3mmol of (E) -4- (3-oxo-3- (2- (phenylethynyl) phenyl) prop-1-en-1-yl) benzonitrile, 0.06mmol of ferric chloride, and 0.9mmol of diiodo pentoxide were put into a 15mL thick-walled pressure-resistant reaction tube, and 3mL of dichloromethane was added as a solvent. Then, the mixture was magnetically stirred at 100 ℃ for 0.5 hour. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (petroleum ether/ethyl acetate ═ 20:1 as eluent). The material was a white solid in 43% yield.
Characterization data:1H NMR(500MHz,CDCl3)：δ8.18-8.15(m，1H),8.13-8.10(m，1H),7.83-7.79(m，2H),7.38(d，J＝8.5Hz，2H),7.29-7.25(m，3H),7.14-7.12(m，2H),6.85(d，J＝8.5Hz，2H),3.68(d，J＝5.5Hz，1H),3.44(d，J＝5.5Hz，1H).
13C NMR(125MHz,CDCl3)：δ191.74,190.18,139.06,134.70,134.45,132.19,132.13,131.71,131.68,130.73,128.59,128.44,128.34,128.17,126.87,118.26,111.24,50.71,41.78,39.71.
example 9
0.3mmol of (E) -1- (5-methoxy-2- (phenylethynyl) phenyl) -3-phenylprop-2-en-1-one, 0.06mmol of ferric chloride and 0.9mmol of diiodo pentoxide were put into a 15mL thick-walled pressure-resistant reaction tube, and 3mL of toluene was added as a solvent. Then, the mixture was magnetically stirred at 100 ℃ for 0.5 hour. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (petroleum ether/ethyl acetate ═ 20:1 as eluent). The material was a white solid in 61% yield.
Characterization data:1H NMR(500MHz,CDCl3)：δ8.14(d，J＝8.5Hz),7.55(d，J＝2.5Hz，1H),7.30-7.28(m，1H),7.27-7.24(m，3H),7.17-7.08(m，5H),6.78-6.76(m，2H),3.98(s，3H),3.65(d，J＝6Hz,1H),3.42(d，J＝5.5Hz，1H)
13C NMR(125MHz,CDCl3)：δ192.83,190.20,164.45,134.62,133.61,131.92,131.87,130.57,128.06,128.03,128.03,127.96,127.49,125.74,121.88,109.16,55.98,50.61,43.50,40.05.
example 10
0.3mmol of (E) -1- (4-methyl-2- (phenylethynyl) phenyl) -3- (p-tolyl) prop-2-en-1-one, 0.06mmol of ferric chloride and 0.9mmol of diiodo pentoxide were put into a 15mL thick-walled pressure-resistant reaction tube, and 3mL of 1, 4-dioxane was added as a solvent. Then, the mixture was magnetically stirred at 80 ℃ for 0.5 hour. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (petroleum ether/ethyl acetate ═ 20:1 as eluent). The material was a white solid in 68% yield.
Characterization data:1H NMR(500MHz,CDCl3)：δ8.02(d，J＝8Hz，1H),7.97(s，1H),7.60(dd，J1＝8Hz，J2＝1.5Hz，1H),7.27-7.25(m，3H),7.17-7.15(m，2H),6.90(d，J＝8Hz，2H),6.63(d，J＝8Hz，2H)3.61(d，J＝5.5Hz，1H),3.38(d，J＝5.5Hz，1H),2.53(s，3H),2.23(s，3H).
13C NMR(125MHz,CDCl3)：δ192.75,191.39,145.58,137.25,135.01,132.46,131.94,131.91,130.46,130.22,128.76,128.22,128.03,127.89,126.94,50.88,43.26,40.08,21.87,20.99.
example 11
0.3mmol (E) -3-phenyl-1- (2- (thien-3-ylethynyl) phenyl) prop-2-en-1-one, 0.06mmol ferric chloride, and 0.9mmol diiodo pentoxide were added to a 15mL thick-walled pressure-resistant reaction tube, and 3mL 1, 4-dioxane was added as a solvent. Then, the mixture was magnetically stirred at 120 ℃ for 0.5 hour. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (petroleum ether/ethyl acetate ═ 20:1 as eluent). The material was a white solid in 63% yield.
Characterization data:1H NMR(500MHz,CDCl3)：δ8.21-8.16(m，1H),8.13-8.08(m，1H),7.81-7.76(m，2H),7.18-7.11(m，5H),6.88-6.86(m，3H),3.69(d，J＝6Hz),3.41(d，J＝6Hz，1H)
13C NMR(126MHz,CDCl3)：δ192.44,190.70,134.40,134.18,133.15,132.34,129.88,128.06,127.97,127.86,127.60,126.97,126.76,126.31,125.56,125.06,46.01,43.13,39.89.
example 12
0.3mmol (E) -3-phenyl-1- (2- ((4-propylphenyl) ethynyl) phenyl) prop-2-en-1-one, 0.06mmol ferric chloride and 0.9mmol diiodo pentoxide were added to a 15mL thick-walled pressure-resistant reaction tube, and 3mL 1, 4-dioxane was added as a solvent. Then, the mixture was magnetically stirred at 100 ℃ for 0.1 hour. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (petroleum ether/ethyl acetate ═ 20:1 as eluent). The material was a white solid in 59% yield.
Characterization data:1H NMR(500MHz,CDCl3)：δ8.21-8.16(m，1H),8.13-8.08(m，1H),7.81-7.76(m，2H),7.18-7.11(m，5H),6.88-6.86(m，3H),3.69(d，J＝6Hz),3.41(d，J＝6Hz，1H)
13C NMR(126MHz,CDCl3)：δ192.44,190.70,134.40,134.18,133.15,132.34,129.88,128.06,127.97,127.86,127.60,126.97,126.76,126.31,125.56,125.06,46.01,43.13,39.89.
example 13
0.3mmol (E) -3-phenyl-1- (2- ((4- (trifluoromethyl) phenyl) ethynyl) phenyl) prop-2-en-1-one, 0.06mmol ferric chloride, 0.9mmol diiodo pentoxide were added to a 15mL thick-walled pressure-resistant reaction tube, and 3mL 1, 4-dioxane was added as a solvent. Then, the mixture was magnetically stirred at 100 ℃ for 1.0 hour. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (petroleum ether/ethyl acetate ═ 20:1 as eluent). The material was a white solid in 64% yield.
Characterization data:1H NMR(500MHz,CDCl3):δ8.19-8.16(m，1H),8.15-8.11(m，1H),7.83-7.80(m，2H),7.52(d，J＝8Hz，2H),7.29(d，J＝8Hz，2H),7.17-7.11(m，3H),6.79-6.77(m，2H),3.71(d，J＝5.5Hz，1H),3.50(d，J＝5.5Hz，1H)
13C NMR(125MHz,CDCl3)：δ192.08,190.35,135.84,134.59,134.46,132.67,132.40,132.28,132.22,130.19(dd，J1＝65Hz，J2＝32.5Hz),128.32,128.09,127.90,126.91,125.00,124.97,124.95,122.86,50.22,42.84,39.26.
example 14
0.3mmol of (E) -3- (2-fluorophenyl) -1- (2- (phenylethynyl) phenyl) prop-2-en-1-one, 0.06mmol of ferric chloride and 1.2mmol of diiodo pentoxide were put into a 15mL thick-walled pressure-resistant reaction tube, and 3mL of 1, 4-dioxane was added as a solvent. Then, the mixture was magnetically stirred at 100 ℃ for 0.5 hour. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain a pure product represented by the structural formula (petroleum ether/ethyl acetate ═ 20:1 as eluent). The material was a white solid in 66% yield.
Characterization data:1H NMR(500MHz,CDCl3):δ8.22-8.18(m，1H),8.14-8.10(m，1H),7.84-7.78(m，2H),7.27-7.20(m，5H),7.14-7.09(m，1H),7.01,-6.97(m，1H),6.80-6.77(m，1H),6.49-6.46(m，1H),3.74(d，J＝6Hz，1H),3.66(d，J＝6Hz，1H).
13C NMR(126MHz,CDCl3)：δ192.62,190.86,161.78(d，J＝232.5Hz),134.40(d，J＝45Hz),132.42(d，J＝17.5Hz),131.55,131.40,129.20(d，J＝7.5Hz),128.16,128.10,128.07,127.75(d，J＝2.5Hz),126.74,123.65(d，J＝3.75Hz),121.00,120.89,115.12(d，J＝21.25Hz),49.65,37.93,36.20(d，J＝6.25)
example 15
0.3mmol of (E) -1- (2- ((2-fluorophenyl) ethynyl) phenyl) -3-phenylprop-2-en-1-one, 0.015mmol of ferric chloride and 0.6mmol of diiodo pentoxide are added into a 15mL thick-walled pressure-resistant reaction tube, and 3mL of 1, 4-dioxane is added as a solvent. Then, the mixture was magnetically stirred at 100 ℃ for 0.5 hour. After cooling to room temperature, two-spoon column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure, followed by column chromatography to obtain the pure product (petroleum ether/ethyl acetate 20:1 as eluent). The material was a white solid in 40% yield.
Characterization data:1H NMR(500MHz,CDCl3)：δ8.19-8.16(m，1H),8.13-8.10(m，1H),7.83-7.79(m，2H),7.30-7.25(m，1H),7.18-7.07(m，5H)，6.93(t，J＝9Hz，1H),6.85(d，J＝7.5Hz),3.66(d，J＝6Hz，1H),3.52(d，J＝6Hz，1H).
13C NMR(125MHz,CDCl3)：δ192.34,190.06,162.17(d，J＝248.5Hz),134.42(d，J＝25Hz),134.35(d，J＝30.63Hz),133.15,132.44(d，J＝7.8Hz),130.36(d，J＝8.3Hz),128.93,128.72,128.07,127.99,127.78,127.69,126.78,123.81(d，J＝2.9Hz),119.88(d，J＝14.8Hz),115.59(d，J＝21.4Hz),42.64,39.53,29.66.
Claims (10)
1. a method for synthesizing a 1, 4-naphthoquinocyclopropane compound shown in a formula (II) is characterized by comprising the following steps: taking an o-alkynyl chalcone compound shown in a formula (I) as an initiator, taking ferric chloride or ferric nitrate as a catalyst, reacting in a solvent at the temperature of 80-120 ℃ for 0.1-1.0h under the condition that diiodo pentoxide or iodobenzene diacetate is taken as an oxidant, and separating and purifying to obtain a 1, 4-naphthoquinone cyclopropane compound shown in a formula (II);
（Ⅰ） （Ⅱ）
in formula (I) or formula (II), R1Is phenyl, 2-fluorophenyl, 3-chlorophenyl, 4-bromophenyl, 2-methylbenzene, 4-methylphenyl, 2-methoxyphenyl or 4-cyanophenyl, thienyl, R2Is H, methyl or methoxy, R3Is phenyl, 4-propylphenyl, 2-fluorophenyl or 4-trifluoromethylphenyl.
2. The process for synthesizing a 1, 4-naphthoquinocyclopropane compound represented by the formula (ii) according to claim 1, which comprises: the amount of the catalyst substance is 5-30% of the amount of the ortho-alkynyl chalcone compound substance shown in the formula (I).
3. The process for synthesizing a 1, 4-naphthoquinocyclopropane compound represented by the formula (II) according to any one of claims 1 to 2, which comprises: the amount of the oxidant is 100-400% of the amount of the o-alkynyl chalcone compound shown in the formula (I).
4. The process for synthesizing a 1, 4-naphthoquinocyclopropane compound represented by the formula (ii) according to claim 1, which comprises: the solvent is one or more of acetonitrile, tetrahydrofuran, dichloromethane, toluene and 1, 4-dioxane.
5. The process for synthesizing a 1, 4-naphthoquinocyclopropane compound represented by the formula (ii) according to claim 1, which comprises: the volume of the solvent is 5-10 mL/mmol based on the amount of the ortho-alkynyl chalcone compound shown in the formula (I).
6. The process for synthesizing a 1, 4-naphthoquinocyclopropane compound represented by the formula (ii) according to claim 1, which comprises: the reaction temperature of the reaction was 100 ℃.
7. The process for synthesizing a 1, 4-naphthoquinocyclopropane compound represented by the formula (ii) according to claim 1, which comprises: the reaction time of the reaction was 0.5 h.
8. The process for the synthesis of 1, 4-naphthoquinocyclopropane compounds of formula (ii) according to claim 1, wherein said separation and purification is: adding column chromatography silica gel into the reaction liquid, removing the solvent through reduced pressure distillation, separating through column chromatography, eluting by using a mixed liquid of petroleum ether and ethyl acetate with the volume ratio of 20:1 as an eluent, collecting the eluent containing the target product, and evaporating the solvent to obtain the 1, 4-naphthoquinone cyclopropane compound shown in the formula (II).
9. The process for synthesizing a 1, 4-naphthoquinocyclopropane compound represented by the formula (ii) according to claim 8, which comprises: the column chromatography silica gel is 100-200 meshes.
10. The process for synthesizing a 1, 4-naphthoquinocyclopropane compound represented by the formula (ii) according to claim 8, which comprises: the mass of the column chromatography silica gel is 0.5 g.
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| CN114702399A (en) * | 2022-05-05 | 2022-07-05 | 信阳师范学院 | 2-trifluoroalkyl-1, 4-naphthoquinone compound and synthetic method thereof |
| CN115028591B (en) * | 2022-06-17 | 2024-05-28 | 内江金鸿曲轴有限公司 | Anthraquinone compound and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965034A (en) * | 2014-03-18 | 2014-08-06 | 浙江工业大学 | Synthetic method of indanone and derivative of indanone |
| CN106316817A (en) * | 2015-06-19 | 2017-01-11 | 浙江工业大学 | Synthetic method for 2-substituted-1,4-naphthoquinone derivatives |
-
2017
- 2017-12-08 CN CN201711293856.2A patent/CN109896944B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965034A (en) * | 2014-03-18 | 2014-08-06 | 浙江工业大学 | Synthetic method of indanone and derivative of indanone |
| CN106316817A (en) * | 2015-06-19 | 2017-01-11 | 浙江工业大学 | Synthetic method for 2-substituted-1,4-naphthoquinone derivatives |
Non-Patent Citations (2)
| Title |
|---|
| Catalytic Sulfur-Enabled Dehydrobicyclization of 1,6-Enynes toward Arylated Indeno[1,2-c]thiophenes;Wang ZhiQiang等;《Journal of Organic Chemistry》;20160513;第81卷(第11期);第4762-4770页 * |
| Cu(0)/Selectfluor System-Mediated Mild Synthesis of Fluorinated Fluorenones from Nonaromatic Precursors (1,6-Enynes) Involving C-C Single Bond Cleavage;Zhang Jian等;《Organic Letters》;20150529;第17卷(第12期);第2920-2923页 * |
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