CN109293550A - One kind containing trifluoromethyl 3,6 '-asymmetric double benzazolyl compounds and its synthetic method - Google Patents
One kind containing trifluoromethyl 3,6 '-asymmetric double benzazolyl compounds and its synthetic method Download PDFInfo
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- CN109293550A CN109293550A CN201811407604.2A CN201811407604A CN109293550A CN 109293550 A CN109293550 A CN 109293550A CN 201811407604 A CN201811407604 A CN 201811407604A CN 109293550 A CN109293550 A CN 109293550A
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- trifluoromethyl
- asymmetric double
- benzazolyl compounds
- synthetic method
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- -1 benzazolyl compounds Chemical class 0.000 title claims abstract description 63
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 title claims abstract description 43
- 238000010189 synthetic method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 12
- FQODPPSFOYMQMV-UHFFFAOYSA-N FC=1C(=C2C(=C(NC2=CC1)C)F)F Chemical compound FC=1C(=C2C(=C(NC2=CC1)C)F)F FQODPPSFOYMQMV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000010898 silica gel chromatography Methods 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 45
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052733 gallium Inorganic materials 0.000 claims description 14
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical class C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- KOCDJSLUDZGVJX-UHFFFAOYSA-N indium;trifluoromethanesulfonic acid Chemical compound [In].OS(=O)(=O)C(F)(F)F KOCDJSLUDZGVJX-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- ZLQBNKOPBDZKDP-UHFFFAOYSA-L nickel(2+);diperchlorate Chemical compound [Ni+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZLQBNKOPBDZKDP-UHFFFAOYSA-L 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- QUJLPICXDXFRSN-UHFFFAOYSA-N scandium;trifluoromethanesulfonic acid Chemical compound [Sc].OS(=O)(=O)C(F)(F)F QUJLPICXDXFRSN-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- MRVDPBDPQPBGMS-UHFFFAOYSA-N trifluoromethanesulfonic acid;yttrium Chemical compound [Y].OS(=O)(=O)C(F)(F)F MRVDPBDPQPBGMS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 abstract description 10
- 239000003814 drug Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 229940079593 drug Drugs 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000012827 research and development Methods 0.000 abstract description 2
- 239000011968 lewis acid catalyst Substances 0.000 abstract 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 33
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 150000002475 indoles Chemical class 0.000 description 12
- 229960004217 benzyl alcohol Drugs 0.000 description 11
- 235000019445 benzyl alcohol Nutrition 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 239000003480 eluent Substances 0.000 description 10
- HQHRJIAWNUYFCA-UHFFFAOYSA-N fluoromethane 1H-indole Chemical class CF.C1=CC=C2C(=C1)C=CN2 HQHRJIAWNUYFCA-UHFFFAOYSA-N 0.000 description 10
- 239000003208 petroleum Substances 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- 229960001866 silicon dioxide Drugs 0.000 description 9
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical class C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- KYTDBKDWDOVRLJ-FQBRJNOBSA-N 1,2-dihydro-2,11-epoxycephalotaxine Chemical compound O1C(OC)([C@H]([C@H]2C3=C4)O)C[C@]52CCCN5CC1C3=CC1=C4OCO1 KYTDBKDWDOVRLJ-FQBRJNOBSA-N 0.000 description 1
- TYGUTURXHKSOBP-UHFFFAOYSA-N 10-bromo-5,12-dihydroindolo[2,3-g]carbazole-2,3-diol Chemical compound C1=C(Br)C=C2NC3=C(C4=C(C=C(C(=C4)O)O)N4)C4=CC=C3C2=C1 TYGUTURXHKSOBP-UHFFFAOYSA-N 0.000 description 1
- ZTNBSFMIFOLVCM-UHFFFAOYSA-N 20S-Dimethylamino-3alpha-methoxypregn-5-ene Natural products C12CCC3(C)C(C(C)N(C)C)CCC3C2CC=C2C1(C)CCC(OC)C2 ZTNBSFMIFOLVCM-UHFFFAOYSA-N 0.000 description 1
- PZZXYDQKZIGACT-UHFFFAOYSA-N 5-hydroxyskytanthine Natural products C1N(C)CC(C)C2(O)C1C(C)CC2 PZZXYDQKZIGACT-UHFFFAOYSA-N 0.000 description 1
- 229940124321 AIDS medicine Drugs 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- RTHCYVBBDHJXIQ-UHFFFAOYSA-N N-methyl-3-phenyl-3-[4-(trifluoromethyl)phenoxy]propan-1-amine Chemical compound C=1C=CC=CC=1C(CCNC)OC1=CC=C(C(F)(F)F)C=C1 RTHCYVBBDHJXIQ-UHFFFAOYSA-N 0.000 description 1
- 108050002826 Neuropeptide Y Receptor Proteins 0.000 description 1
- 102000012301 Neuropeptide Y receptor Human genes 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- 229960004373 acetylcholine Drugs 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000000794 anti-serotonin Effects 0.000 description 1
- 239000003420 antiserotonin agent Substances 0.000 description 1
- 206010003246 arthritis Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BVLXNPRUOXPBII-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)gallanyl trifluoromethanesulfonate Chemical compound [Ga+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F BVLXNPRUOXPBII-UHFFFAOYSA-K 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940047495 celebrex Drugs 0.000 description 1
- RZEKVGVHFLEQIL-UHFFFAOYSA-N celecoxib Chemical compound C1=CC(C)=CC=C1C1=CC(C(F)(F)F)=NN1C1=CC=C(S(N)(=O)=O)C=C1 RZEKVGVHFLEQIL-UHFFFAOYSA-N 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229930185377 mucronatin Natural products 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229940035613 prozac Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
Abstract
The present invention provides one kind to contain trifluoromethyl 3,6 '-asymmetric double benzazolyl compounds and its synthetic method, trifluoro methyl indole first alcohol compound, 2- substituted indole, Lewis acid catalyst are added in a solvent, it carries out paying-gram alkylated reaction, thin plate chromatography tracking reaction is until the reaction is complete, then by reaction solution concentrated by rotary evaporation, and target product is obtained containing trifluoromethyl 3 by silica gel column chromatography, 6 '-asymmetric double benzazolyl compounds, this contains the quaternary carbon center that there is 3,6 '-asymmetric double benzazolyl compounds of trifluoromethyl trifluoromethyl to replace.Entire reaction is carried out using " one kettle way ", and easy to operate efficient, yield is higher and reaction substrate range is wide.Containing 3,6 '-asymmetric double benzazolyl compounds of trifluoromethyl made from research and development has potential source biomolecule activity, by follow-up test or can be modified as drug.
Description
Technical field
The invention belongs to chemosynthesis technical fields, and in particular to a kind of 3,6 '-asymmetric double indoles containing trifluoromethyl
Close object and its synthetic method.
Background technique
Benzazole compounds are a kind of important alkaloids, are widely present in natural products.Bis-indole compounds are made
For an important branch of Benzazole compounds, structure contains there are two indoles and with a series of spies of Benzazole compounds
Property, it is widely used in the fields such as medicine and material.For example, natural products mucronatins A and B show acetylcholine ester
Enzyme inhibition activity；The bisindole alkaloid C and D isolated from the sponge of New Caledonia shows antiserotonin activity, right
Serine amicine and neuropeptide Y receptor have very strong activity.Currently, the synthesis of symmetrical bis-indole compounds by
It explores extensively, and is applied to many fields.In contrast, its pharmacology of asymmetric double Benzazole compounds also causes greatly to close
Note, but reported about its study on the synthesis less.
Currently, mainly synthesizing asymmetric double indoles by pair-gram alkylated reaction of 3- indole-alcohol and different indoles
Compound (Tetrahedron, 2005,61 (43): 10235-10241；Green Chemistry,2016,18(4):1032-
1037), but such methods are only applicable to 3,3 '-asymmetric double benzazolyl compounds of synthesis.
Other groups in the alternative drug molecule of fluoro-containing group can significantly improve the medical value and property of drug
Energy.Contain trifluoromethyl (- CF3) compound be widely applied in terms of drug, pesticide, material and dyestuff.For example,
Treat dysthymic drug Prozac, the drug Celebrex for the treatment of of arthritis and anti-AIDS drug Efavirena etc. all
Contain trifluoromethyl.But preparing for fluorine-containing heterocycles is relatively difficult, the research report in relation to its synthesis is less.
Asymmetric double Benzazole compounds and fluorochemical all have significant effect in field of medicaments, by trifluoromethyl
Potential medical value will be had by being introduced into bis-indole compounds.Secondly, the position indoles C-6 expression activitiy is low and needs to borrow
The effect for helping suitable homing device and catalyst, for the successful example of c h bond activation or function dough on the position indoles C-6
It is sub few.
Currently, it is confined to the synthesis of 3,3 '-asymmetric double benzazolyl compounds mostly for the research of asymmetric double indoles, and
Seldom to the study on the synthesis of 3,6 '-asymmetric double benzazolyl compounds, only an example document report can realize synthesis 3 at present, and 6 '-is non-
Symmetric double indoles (Angew.Chem.Int.Ed.2018,57:11004-11008), the document use 6- indoles benzylalcohol and indoles
Paid under phosphoric acid catalyzed-a gram alkylated reaction obtains 3,6 '-asymmetric double indoles, but the raw material of this method is not easy to prepare, and
The three-level carbon center that only there are the product of synthesis double indoles to replace, cannot access double indoles chemical combination with quaternary carbon center
Object.
Summary of the invention
It is an object of the invention to solve in the prior art in synthesis benzazolyl compounds containing trifluoromethyl 3,6 '-asymmetric double
The deficiency of aspect provides a kind of containing 3,6 '-asymmetric double benzazolyl compounds of trifluoromethyl and its synthetic method.This is 3,6 '-non-right
The quaternary carbon center for claiming bis-benzazolyl compounds that there is trifluoromethyl to replace, and preparation method has wide application range of substrates, simplicity
The advantages that efficient.
To achieve the above object, the present invention provides the following technical scheme that
A kind of 3,6 '-asymmetric double benzazolyl compounds containing trifluoromethyl, shown in structural formula such as formula (I):
Wherein, R1、R2、R3For group independent, R1Selected from halogen atom, methoxyl group, methyl, ester group, hydroxyl or alkane
One of base；R2Selected from one of phenyl, halogen substituted phenyl, alkyl-substituted phenyl or naphthalene；R3Selected from phenyl, cycloalkanes
One kind of base or alkyl.
The synthetic method of the above-mentioned benzazolyl compounds Han trifluoromethyl 3,6 '-asymmetric double: with trifluoro methyl indole methanol class
Compound and 2- substituted indole are that raw material is reacted in a solvent under the action of catalyst, reaction product rotate dense
Contracting, then by 200~300 mesh silica gel column chromatographies separate to get.
Reaction equation is as follows:
Further, shown in the structural formula such as formula (II) of the trifluoro methyl indole first alcohol compound:
R in formula (II)1、R2R in same formula (I)1、R2It is corresponding consistent.
Further, shown in the structural formula such as formula (III) of the 2- substituted indole:
R in formula (III)3R in same formula (I)3It is corresponding consistent.
Further, the catalyst is selected from ferric trichloride [FeCl3], nickelous perchlorate [Ni (ClO4)2], gallium triflate
[Ga(OTf)3], trifluoromethanesulfonic acid yttrium [Y (OTf)3], trifluoromethanesulfonic acid indium [In (OTf)3] or trifluoromethanesulfonic acid scandium [Sc
(OTf)3] in any one, preferably gallium triflate, catalytic effect are best.
Further, the solvent be acetonitrile, dichloroethanes, toluene, tetrahydrofuran, methyl tertiary butyl ether(MTBE), nitromethane or
Any one in glycol dimethyl ether, preferably acetonitrile, yield are best.
Further, the molar ratio of the trifluoro methyl indole first alcohol compound and 2- substituted indole is 1:1.5.
Further, the molar ratio of the catalyst and trifluoro methyl indole first alcohol compound is (0.01-0.1): 1.
Further, the reaction temperature is 80 DEG C, and the reaction time is 24-48 hours.
One kind of synthetic method as the benzazolyl compounds of the present invention Han trifluoromethyl 3,6 '-asymmetric double is preferably
Scheme, concentration of the trifluoro methyl indole first alcohol compound in acetonitrile is 0.1mol/L.
Beneficial effects of the present invention:
(1) the present invention provides a kind of 3,6 '-asymmetric double benzazolyl compounds containing trifluoromethyl, and are successfully realized its
Synthesis.
(2) present invention is using Benzazole compounds as raw material, and suitable substrates range is wider, and various functional group tolerances are relatively
It is good.
(3) synthetic method of the invention is easy to operate, and yield is higher.
(4) 3, the 6 '-asymmetric double benzazolyl compounds of trifluoromethyl that contain of the invention have reactivity, have potential raw
Object activity and medical value.
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of the 1aa Han trifluoromethyl 3,6 '-asymmetric double benzazolyl compounds made from embodiment 1；
Fig. 2 is the nuclear-magnetism carbon spectrogram of the 1aa Han trifluoromethyl 3,6 '-asymmetric double benzazolyl compounds made from embodiment 1；
Fig. 3 is the nuclear-magnetism fluorine spectrogram of the 1aa Han trifluoromethyl 3,6 '-asymmetric double benzazolyl compounds made from embodiment 1；
Fig. 4 is the single crystal diffraction figure of the 1aa Han trifluoromethyl 3,6 '-asymmetric double benzazolyl compounds made from embodiment 1.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, right combined with specific embodiments below
A specific embodiment of the invention is described in detail.
In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention, but the present invention can be with
Implemented using other than the one described here other way, those skilled in the art can be without prejudice to intension of the present invention
In the case of do similar popularization, therefore the present invention is not limited by the specific embodiments disclosed below.
Embodiment 1:
Reaction equation are as follows:
The synthetic method of 3, the 6 '-asymmetric double benzazolyl compounds containing trifluoromethyl: 25mL round-bottomed flask is taken, sequentially adds three
Methyl fluoride indoles benzylalcohol 2a (0.3mmol), 2-phenylindone 3a (0.45mmol), gallium triflate (0.03mmol) and acetonitrile
(3 milliliters) stir 48 hours at 80 DEG C, then carry out concentrated by rotary evaporation to reaction mixture, then pass through 200~300 mesh silica gel
Column chromatography for separation, eluant, eluent used are ethyl acetate: petroleum ether=6:100, and isolated target product 1aa (120.4mg, it is white
Color solid, yield 86%).
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of 1 compound 1aa of the embodiment of the present invention；Fig. 2 is 1 compound 1aa's of the embodiment of the present invention
Nuclear-magnetism carbon spectrogram；Fig. 3 is the nuclear-magnetism fluorine spectrogram of 1 compound 1aa of the embodiment of the present invention；Fig. 4 is 1 compound of the embodiment of the present invention
The single crystal diffraction figure of 1aa.
1H NMR(600MHz,CDCl3): δ 8.03 (s, 1H), 7.93 (s, 1H), 7.58 (d, J=8.1Hz, 3H), 7.50-
7.18 (m, 13H), 7.15 (d, J=8.2Hz, 1H), 6.99 (t, J=7.6Hz, 1H), 6.83 (s, 1H), 6.59 (s, 1H)
13C NMR(150MHz,CDCl3):δ140.5,138.9,136.7,136.5,133.9,132.2,129.8,
129.0,128.3,128.0,127.9,127.5,127.1,126.5,125.2,122.7,122.2,120.0,199.9；
(116.6,112.9,111.25,99.5,60.8 q, J=25.2Hz)
Embodiment 2:
Reaction equation are as follows:
The synthetic method of 3, the 6 '-asymmetric double benzazolyl compounds containing trifluoromethyl: 25mL round-bottomed flask is taken, sequentially adds three
Methyl fluoride indoles benzylalcohol 2b (0.5mmol), 2-phenylindone 3a (0.75mmol), gallium triflate (0.05mmol) and acetonitrile
(3 milliliters) stir 48 hours at 80 DEG C.Then concentrated by rotary evaporation is carried out to reaction mixture, then passes through 200~300 mesh silicagel columns
Chromatography, eluant, eluent used are ethyl acetate: petroleum ether=6:100, isolated target product 1ba (234.1mg, white
Solid, yield 81%).
1H NMR(600MHz,DMSO-d6): δ 11.58 (s, 1H), 11.53 (s, 1H), 7.84 (d, 2H, J=7.6Hz),
7.56 (d, 1H, J=8.5Hz), 7.50 (d, 1H, J=8.6Hz), 7.46-7.41 (m, 5H), 7.32-7.28 (m, 3H), 7.20
(s, 1H), 7.11 (d, 1H, J=8.3Hz), 7.02 (d, 1H, J=8.3Hz), 6.94 (s, 1H), 6.87 (s, 1H), 6.73 (s,
1H).
13C NMR(150MHz,DMSO-d6):δ140.2,139.3,137.2,135.9,132.5,132.4,129.6,
129.5,129.4,128.7,128.3,128.3,128.0,127.4,125.4,124.1,121.8,121.1,120.1,
(114.4,114.1,113.0,98.8,60.5 q, J=24.0Hz)
Embodiment 3:
Reaction equation are as follows:
The synthetic method of 3, the 6 '-asymmetric double benzazolyl compounds containing trifluoromethyl: 25mL round-bottomed flask is taken, sequentially adds three
Methyl fluoride indoles benzylalcohol 2c (0.2mmol), 2-phenylindone 3a (0.3mmol), gallium triflate (0.02mmol) and acetonitrile
(3 milliliters) stir 24 hours at 80 DEG C.Then concentrated by rotary evaporation is carried out to reaction mixture, then passes through 200~300 mesh silicagel columns
Chromatography, eluant, eluent used are ethyl acetate: petroleum ether=20:100, isolated target product 1ca (117.3mg, white
Solid, yield 90%).
1H NMR(600MHz,CDCl3) δ=8.70 (s, 1H), 8.39 (s, 1H), 7.64 (d, 2H, J=3.0Hz), 7.59
(d, 1H, J=8.5Hz), 7.52 (s, 1H), 7.46-7.43 (m, 3H), 7.40-7.32 (m, 6H), 7.28 (s, 1H), 7.25 (m,
6H), 7.17 (d, 1H, J=8.5Hz), 6.85 (d, 1H, J=1.4Hz), 6.82 (d, 1H, J=2.6Hz)
13C NMR(150MHz,CDCl3)δ139.7,139.3,138.6,136.6,133.1,132.1,129.6,129.4,
129.1,128.6,128.3,128.1,128.0 (d, J=6.7Hz), 126.17,125.27,125.04,121.90,120.80,
(120.2,117.6,112.51,112.5,102.9,99.5,60.5 q, J=24.2Hz)
Embodiment 4:
Reaction equation are as follows:
The synthetic method of 3, the 6 '-asymmetric double benzazolyl compounds containing trifluoromethyl: 25mL round-bottomed flask is taken, sequentially adds three
Methyl fluoride indoles benzylalcohol 2d (0.5mmol), 2-phenylindone 3a (0.75mmol), gallium triflate (0.05mmol) and acetonitrile
(3 milliliters) stir 48 hours at 80 DEG C.Then concentrated by rotary evaporation is carried out to reaction mixture, then passes through 200~300 mesh silicagel columns
Chromatography, eluant, eluent used are ethyl acetate: petroleum ether=6:100, isolated target product 1da (139.4mg, white
Solid, yield 81%).
1H NMR(600MHz,CDCl3): δ 8,25 (s, 1H), 8.06 (s, 1H), 7.63 (d, 2H, J=7.8Hz), 7.59
(d, 1H, J=8.5Hz), 7.46-7.41 (m, 4H), 7.35-7.33 (m, 4H), 7.29 (d, 2H, J=8.8Hz), 7.25 (d,
1H, J=8.6Hz), 6.86-6.83 (m, 2H), 6.76 (s, 1H), 6.38 (s, 1H), 3.50 (s, 3H)
13C NMR(150MHz,CDCl3):δ153.8,140.4,138.9,136.6,133.8,132.2,131.7,
129.9,129.0,128.3,128.0,127.8,127.5,127.2,127.1,125.1,122.3,119.9,116.1,
(112.8,112.5,111.7,104.1,99.5,61.4 q, J=24.8Hz), 55.51.
Embodiment 5:
Reaction equation are as follows:
The synthetic method of 3, the 6 '-asymmetric double benzazolyl compounds containing trifluoromethyl: 25mL round-bottomed flask is taken, sequentially adds three
Methyl fluoride indoles benzylalcohol 2e (0.3mmol), 2-phenylindone 3a (0.45mmol), gallium triflate (0.03mmol) and acetonitrile
(3 milliliters) stir 48 hours at 80 DEG C.Then concentrated by rotary evaporation is carried out to reaction mixture, then passes through 200~300 mesh silicagel columns
Chromatography, eluant, eluent used are ethyl acetate: petroleum ether=6:100, isolated target product 1ea (127.5mg, white
Solid, yield 80%).
1H NMR(400MHz,DMSO-d6):δ16.32(s,1H),16.10(s,1H),12.60-12.54(m,3H),
12.44-12.31 (m, 4H), 12.24-12.17 (m, 3H), 12.01 (t, 1H, J=7.4Hz), 11.95 (s, 1H), 11.86 (t,
1H, J=18.6Hz), 11.77 (d, 1H, J=8.7Hz), 11.69 (d, 1H, J=1.4Hz), 11.63-11.53 (m, 3H)
13C NMR(100MHz,DMSO-d6):δ146.6,144.2,142.2,141.9,138.7,137.2,136.8,
134.7,134.3,134.1,133.9,133.2,132.8,132.6,130.8,130.6,130.5,130.2,129.9,
127.9,126.6,126.0,125.8,125.0,124.4,118.5,117.8,117.3,10 3.6,65.5 (q, J=
24.4Hz).
Embodiment 6:
The synthetic method of 3, the 6 '-asymmetric double benzazolyl compounds containing trifluoromethyl: 25mL round-bottomed flask is taken, sequentially adds three
Methyl fluoride indoles benzylalcohol 2f (0.5mmol), 2-phenylindone 3a (0.75mmol), gallium triflate (0.05mmol) and acetonitrile
(3 milliliters) stir 48 hours at 80 DEG C.Then concentrated by rotary evaporation is carried out to reaction mixture, then passes through 200~300 mesh silicagel columns
Chromatography, eluant, eluent used are ethyl acetate: petroleum ether=8:100, isolated target product 1fa (176.1mg, white
Solid, yield 73%).
1H NMR(600MHz,CDCl3): δ 7.90 (1s, 1H), 7.80 (1s, 1H), 7.61 (d, 1H, J=8.5Hz), 7.55
(d, 2H, J=7.3Hz), 7.45 (t, 2H, J=7.6Hz), 7.38-7.24 (m, 8H), 7.13 (t, 2H, J=8.2Hz), 7.04
(t, 1H, J=8.1Hz), 6.86 (s, 1H), 6.54 (s, 1H), 2.42 (s, 3H)
13C NMR(150MHz,CDCl3)δ138.9,137.5,137.3,136.8,136.5,134.1,132.1,129.7,
129.4,129.1,128.9,128.2,127.9,127.5,127.2,126.6,125.3,122.7,122.2,120.0,
(119.9,116.7,113.0,111.4,99.5,60.5 q, J=25.0Hz), 21.1.
Embodiment 7:
The synthetic method of 3, the 6 '-asymmetric double benzazolyl compounds containing trifluoromethyl: 25mL round-bottomed flask is taken, sequentially adds three
Methyl fluoride indoles benzylalcohol 2g (0.5mmol), 2-phenylindone 3a (0.75mmol), gallium triflate (0.05mmol) and acetonitrile
(3 milliliters) stir 48 hours at 80 DEG C.Then concentrated by rotary evaporation is carried out to reaction mixture, then passes through 200~300 mesh silicagel columns
Chromatography, eluant, eluent used are ethyl acetate: petroleum ether=6:100, isolated target product 1ga (129.7mg, white
Solid, yield 50%).
1H NMR(400MHz,CDCl3): δ 7.96 (s, 1H), 7.89 (s, 1H), 7.79 (t, 2H, J=8.0Hz), 7.69
(d, 1H, J=8.8Hz), 7.57-7.45 (m, 6H), 7.41-7.17 (m, 9H), 6.93 (t, 1H, J=8.0Hz), 6.79 (d,
1H, J=1.32Hz), 6.48 (d, 1H, J=2.5Hz)
13C NMR(100MHz,CDCl3)δ139.0,138.0,136.78,136.5,133.9,132.8,132.5,
132.1,129.0,128.7,128.4,127.9,127.7,127.4,127.3,126.5,126.5,126.1,125.2,
(122.7,122.2,120.0,119.9,116.5,112.9,111.3,99.5,61.0 q, J=24.9Hz)
Embodiment 8:
The synthetic method of 3, the 6 '-asymmetric double benzazolyl compounds containing trifluoromethyl: 25mL round-bottomed flask is taken, sequentially adds three
Methyl fluoride indoles benzylalcohol 2a (0.3mmol), 2-phenylindone 3b (0.45mmol), gallium triflate (0.03mmol) and acetonitrile
(3 milliliters) stir 36 hours at 80 DEG C.Then concentrated by rotary evaporation is carried out to reaction mixture, then passes through 200~300 mesh silicagel columns
Chromatography, eluant, eluent used are ethyl acetate: petroleum ether=6:100, isolated target product 1ab (130.9mg, white
Solid, yield 82%).
1H NMR(400MHz,CDCl3): δ 7.53 (s, 1H), 7.43 (d, 2H, J=8.4Hz), 7.26-7.08 (m, 9H),
6.96-6.91(m,2H),6.25(s,1H),6.21(s,1H),1.27(s,9H).
13C NMR(100MHz,CDCl3)δ150.1,140.8,136.8,135.5,132.9,129.9,129.8,128.0,
127.5,127.4,127.0,126.6,122.8,122.8,122.1,121.5,119.8,119.3,116.8,112.5,
111.3,96.7,60.8 (q, J=24.9Hz), 31.9,30.3
Embodiment 9:
The synthetic method of 3, the 6 '-asymmetric double benzazolyl compounds containing trifluoromethyl: 25mL round-bottomed flask is taken, sequentially adds three
Methyl fluoride indoles benzylalcohol 2a (0.3mmol), 2-phenylindone 3c (0.45mmol), gallium triflate (0.03mmol) and acetonitrile
(3 milliliters) stir 24 hours at 80 DEG C.Then concentrated by rotary evaporation is carried out to reaction mixture, then passes through 200~300 mesh silicagel columns
Chromatography, eluant, eluent used are ethyl acetate: petroleum ether=8:100, isolated target product 1ac (144.8mg, white
Solid, yield 80%).
1H NMR(400MHz,CDCl3): δ 7.63 (s, 1H), 7.33 (d, 1H, J=8.5Hz), 7.22-7.20 (m, 10H),
7.14-7.03 (m, 10H), 6.88 (t, 1H, J=6.9Hz), 6.84 (s, 1H), 6.32 (s, 1H), 5.95 (s, 1H), 5.37 (s,
1H).
13C NMR(100MHz,CDCl3)δ141.9,140.6,136.7,135.8,133.2,129.9,129.0,129.0,
128.6,127.9,127.3,127.3,127.2,126.9,126.5,122.7,122.1,12 1.6,119.6 (d, J=
33.5Hz), 116.7,112.7,111.2,102.4,60.7 (q, J=25.0Hz), 51.1.
Embodiment 10:
The synthetic method of 3, the 6 '-asymmetric double benzazolyl compounds containing trifluoromethyl: 25mL round-bottomed flask is taken, sequentially adds three
Methyl fluoride indoles benzylalcohol 2a (0.2mmol), 2-phenylindone 3c (0.3mmol), gallium triflate (0.02mmol) and acetonitrile
(3 milliliters) stir 36 hours at 80 DEG C.Then concentrated by rotary evaporation is carried out to reaction mixture, then passes through 200~300 mesh silicagel columns
Chromatography, eluant, eluent used are ethyl acetate: petroleum ether=6:100, and (59.4mg, white are solid by isolated target product 1ad
Body, yield 63%).
1H NMR(600MHz,CDCl3) δ 7.86 (s, 1H), 7.50 (d, 1H, J=8.5Hz), 7.34-7.17 (m, 9H),
7.01 (t, 1H, J=9.0Hz), 6.96 (s, 1H), 6.33 (s, 1H), 6.24 (s, 1H), 2.58 (s, 1H), 2.00 (s, 2H),
1.87 (s, 2H), 1.78 (d, 1H, J=12.8Hz), 1.44-1.40 (m, 4H), 1.35-1.32 (m, 3H)
13C NMR(150MHz,CDCl3)δ146.3,140.8,136.6,135.0,132.4,129.8,129.3,127.9,
127.5,127.4,127.3,126.5,122.8,122.1,121.3,119.8,119.2,116.8,112.5,111.2,96.9,
60.7 (q, J=25.5Hz), 37.3,32.9 (d, J=7.5Hz), 26.2 (d, J=25.5Hz)
It can be seen that the synthesis side of one kind 3,6 '-asymmetric double benzazolyl compounds Han trifluoromethyl provided by the present invention
The function dough of the position indoles C-6 may be implemented in method, and entire reaction is carried out in the way of one kettle way, and easy to operate, yield height is simultaneously
And reaction substrate range is wide, research and development are obtained to have potential source biomolecule activity containing 3,6 '-asymmetric double benzazolyl compounds of trifluoromethyl,
It by follow-up test or can be modified as drug.
It should be noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferable
Embodiment describes the invention in detail, those skilled in the art should understand that, it can be to technology of the invention
Scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered in this hair
In bright scope of the claims.
Claims (10)
1. a kind of 3,6 '-asymmetric double benzazolyl compounds containing trifluoromethyl, which is characterized in that shown in its structural formula such as formula (I):
Wherein, R1、R2、R3For group independent, R1In halogen atom, methoxyl group, methyl, ester group, hydroxyl or alkyl
One kind；R2Selected from one of phenyl, halogen substituted phenyl, alkyl-substituted phenyl or naphthalene；R3Selected from phenyl, naphthenic base or
One kind of alkyl.
2. the synthetic method of 3, the 6 '-asymmetric double benzazolyl compounds Han trifluoromethyl described in claim 1, which is characterized in that with
Trifluoro methyl indole first alcohol compound and 2- substituted indole are that raw material is reacted in a solvent under the action of catalyst, will
Reaction product carry out concentrated by rotary evaporation, then by silica gel column chromatography separation to get；
The catalyst be selected from ferric trichloride, nickelous perchlorate, gallium triflate, trifluoromethanesulfonic acid yttrium, trifluoromethanesulfonic acid indium or
Any one in trifluoromethanesulfonic acid scandium.
3. the synthetic method of 3, the 6 '-asymmetric double benzazolyl compounds as claimed in claim 2 Han trifluoromethyl, which is characterized in that
Shown in the structural formula such as formula (II) of the trifluoro methyl indole first alcohol compound:
R in formula (II)1、R2R in same formula (I)1、R2It is corresponding consistent.
4. the synthetic method of 3, the 6 '-asymmetric double benzazolyl compounds as claimed in claim 2 Han trifluoromethyl, which is characterized in that
Shown in the structural formula such as formula (III) of the 2- substituted indole:
R in formula (III)3R in same formula (I)3It is corresponding consistent.
5. the synthetic method of 3, the 6 '-asymmetric double benzazolyl compounds as claimed in claim 2 Han trifluoromethyl, which is characterized in that
The catalyst is gallium triflate.
6. the synthetic method of 3, the 6 '-asymmetric double benzazolyl compounds as claimed in claim 2 Han trifluoromethyl, which is characterized in that
The solvent is in acetonitrile, dichloroethanes, toluene, tetrahydrofuran, methyl tertiary butyl ether(MTBE), nitromethane or glycol dimethyl ether
Any one.
7. the synthetic method of 3, the 6 '-asymmetric double benzazolyl compounds as claimed in claim 6 Han trifluoromethyl, which is characterized in that
The solvent is acetonitrile.
8. the synthetic method of 3, the 6 '-asymmetric double benzazolyl compounds as claimed in claim 2 Han trifluoromethyl, which is characterized in that
The molar ratio of the trifluoro methyl indole first alcohol compound and 2- substituted indole is 1:1.5.
9. the synthetic method of 3, the 6 '-asymmetric double benzazolyl compounds as claimed in claim 2 Han trifluoromethyl, which is characterized in that
The molar ratio of the catalyst and trifluoro methyl indole first alcohol compound is (0.01-0.1): 1.
10. the synthetic method of 3, the 6 '-asymmetric double benzazolyl compounds Han trifluoromethyl as described in any one of claim 2 to 9,
It is characterized in that, the reaction temperature is 80 DEG C, and the reaction time is 24-48 hours.
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| CN110590759A (en) * | 2019-09-30 | 2019-12-20 | 南京林业大学 | Novel method for aqueous phase synthesis of asymmetric bis-indole compound containing trifluoromethyl thienyl |
| CN113717090A (en) * | 2021-08-31 | 2021-11-30 | 南京林业大学 | Trifluoromethyl-containing all-carbon quaternary carbon center indole acetonitrile compound and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1742007A (en) * | 2003-01-22 | 2006-03-01 | 伊莱利利公司 | Indole-derivative modulators of steroid hormone nuclear receptors |
| CN101316818A (en) * | 2005-11-30 | 2008-12-03 | 弗·哈夫曼-拉罗切有限公司 | 3-amino-1-arylpropyl indoles and aza-substituted indoles |
-
2018
- 2018-11-23 CN CN201811407604.2A patent/CN109293550B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1742007A (en) * | 2003-01-22 | 2006-03-01 | 伊莱利利公司 | Indole-derivative modulators of steroid hormone nuclear receptors |
| CN101316818A (en) * | 2005-11-30 | 2008-12-03 | 弗·哈夫曼-拉罗切有限公司 | 3-amino-1-arylpropyl indoles and aza-substituted indoles |
Non-Patent Citations (2)
| Title |
|---|
| CAIZHEN YUE ET AL.: "Chiral Phosphoric Acid Catalyzed Asymmetric Synthesis of Heterotriarylmethanes from Racemic Indolyl Alcohols", 《ANGEW. CHEM. INT. ED.》 * |
| SHIGERU SASAKI ET AL.: "Bronsted Acid Catalyzed Friedel-Crafts Alkylation Reactions of Trifluoromethyl-α,β-ynones with Indoles", 《SYNLETT》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590759A (en) * | 2019-09-30 | 2019-12-20 | 南京林业大学 | Novel method for aqueous phase synthesis of asymmetric bis-indole compound containing trifluoromethyl thienyl |
| CN113717090A (en) * | 2021-08-31 | 2021-11-30 | 南京林业大学 | Trifluoromethyl-containing all-carbon quaternary carbon center indole acetonitrile compound and preparation method and application thereof |
| CN113717090B (en) * | 2021-08-31 | 2022-04-05 | 南京林业大学 | Trifluoromethyl-containing all-carbon quaternary carbon center indole acetonitrile compound and preparation method and application thereof |
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Denomination of invention: A 3,6 '- asymmetric bis indole compound containing trifluoromethyl and its synthesis method Effective date of registration: 20231031 Granted publication date: 20200925 Pledgee: Bank of China Limited Xiamen Xiang'an sub branch Pledgor: XIAMEN OURUIJIE BIOTECHNOLOGY CO.,LTD. Registration number: Y2023980063461 |