CN106478501B - A kind of preparation method of 2,3,4-trisubstituted quinoline nitrogen oxide compounds - Google Patents
A kind of preparation method of 2,3,4-trisubstituted quinoline nitrogen oxide compounds Download PDFInfo
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- -1 2,3,4-trisubstituted quinoline nitrogen oxide compounds Chemical class 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical class ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 6
- 125000001424 substituent group Chemical group 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract 3
- 239000010941 cobalt Substances 0.000 claims abstract 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000007363 ring formation reaction Methods 0.000 claims abstract 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- UMYVESYOFCWRIW-UHFFFAOYSA-N cobalt;methanone Chemical compound O=C=[Co] UMYVESYOFCWRIW-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical group [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940071536 silver acetate Drugs 0.000 claims description 3
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims description 3
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical group FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- NIEVKYPIXJDDNI-UHFFFAOYSA-N [N]=O.N1=CC=CC2=CC=CC=C12 Chemical class [N]=O.N1=CC=CC2=CC=CC=C12 NIEVKYPIXJDDNI-UHFFFAOYSA-N 0.000 abstract description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 24
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001345 alkine derivatives Chemical class 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 238000010719 annulation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MDKMYVJGFTZTIC-UHFFFAOYSA-N [O].[N].N1=CC=CC2=CC=CC=C12 Chemical class [O].[N].N1=CC=CC2=CC=CC=C12 MDKMYVJGFTZTIC-UHFFFAOYSA-N 0.000 description 2
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001212 derivatisation Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910020257 Cl2F2 Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 102000003820 Lipoxygenases Human genes 0.000 description 1
- 108090000128 Lipoxygenases Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZAIPMKNFIOOWCQ-UEKVPHQBSA-N cephalexin Chemical group C1([C@@H](N)C(=O)N[C@H]2[C@@H]3N(C2=O)C(=C(CS3)C)C(O)=O)=CC=CC=C1 ZAIPMKNFIOOWCQ-UEKVPHQBSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 208000030603 inherited susceptibility to asthma Diseases 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical compound CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006049 ring expansion reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/58—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems with hetero atoms directly attached to the ring nitrogen atom
- C07D215/60—N-oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开了一种2,3,4‑三取代的喹啉氮氧类化合物的制备方法，包括以下步骤：在钴催化剂、添加剂和氧化剂的作用下，硝酮类化合物和炔类化合物在有机溶剂中进行成环反应，反应结束后经过后处理得到所述的喹啉氮氧类化合物。该制备方法采用的原料来源广泛，可以用于合成带各种取代基的喹啉氮氧类化合物，具有重要的应用价值。The invention discloses a preparation method of 2,3,4-trisubstituted quinoline nitroxide compounds, comprising the following steps: under the action of cobalt catalysts, additives and oxidants, nitrone compounds and acetylene compounds are prepared in an organic The ring-forming reaction is carried out in a solvent, and the quinoline nitroxide compound is obtained through post-treatment after the reaction is completed. The preparation method adopts a wide range of raw materials, can be used for synthesizing quinoline nitrogen oxide compounds with various substituents, and has important application value.
Description
Technical field
The invention belongs to organic synthesis fields, more particularly to a kind of system of 2,3,4- trisubstituted quinoline nitrogen oxygen class compounds
Preparation Method.
Background technique
Quinoline nitrogen oxygen class compound has as a kind of important quinoline, property with not oxidized parent compound
Very big difference embodies visibly different chemical reactivity.It has been widely used for medicine, the fields such as catalysis, such as 6
α, the quinoline nitrogen oxygen class compound that alpha, beta-unsaturated ketone replaces have apparent antifungal activity, and union II quinolines oxynitrides is one
The excellent chiral catalyst of kind, can efficiently realize the reduction of aldehyde ketone and alkene.It can also be used as metal-chelator simultaneously, have
Effect ground is realized with various metals to be coordinated, and is also used widely in analytical chemistry field.The quinoline nitrogen oxygen class that 4- alkene replaces
Compound is then important Na, K-ATP zymoexciter.The quinoline nitrogen oxygen class compounds-treatable branch that 2,4 polyfunctional groups replace
Allergy caused by san bronchial asthma and lipoxygenase metabolin.It is some below with typical quinoline nitrogen oxygen class compound knot
The reactive compound of structure:
Quinoline nitrogen oxygen class compound is in pesticide, and dyestuff, polymer industry, cancer research etc. application is also very extensive, can
As auximone, DNA mutagenizing agent, catalyst for esterification reaction, cross linking of epoxy resin promotor, cephalexin ring expansion are urged
Agent etc..
Synthesis of quinoline nitrogen oxygen class compound main method is only based on the oxidation to quinoline in traditional literature report, and
Usually to use the stronger oxidant of some oxidisability.And it is rarely reported using other methods synthesis of quinoline nitrogen oxides.Mirror
In the extensive bioactivity of quinolines oxynitrides and in the extensive use of numerous areas, develop new synthetic method for quinoline
The synthesis of quinoline nitrogen oxygen class compound is necessary.We successfully realize by the nitrone compound that is easy to get of simplicity and
Interior alkynes is a series of poly-substituted quinoline nitrogen oxygen class compounds of Material synthesis.
Summary of the invention
The present invention provides a kind of preparation method of 2,3,4- trisubstituted quinoline nitrogen oxygen class compounds, which is adopted
With new raw material come synthesis of quinoline nitrogen oxygen class compound, there are the wider array of scope of application, 2 obtained, 3,4- trisubstituted quinoline
Nitrogen oxygen class compound can carry out further derivatization.
The preparation method of the trisubstituted quinoline nitrogen oxygen class compound of 2,3,4- of one kind, comprising the following steps:
Under the action of Co catalysts, additive and oxidant, nitrone compound and acetylene compound are in organic solvent
Middle carry out annulation obtains the quinoline nitrogen oxygen class compound after post treatment after reaction；
Shown in the structure of the nitrone compound such as formula (II):
Shown in the structure of the acetylene compound such as formula (III):
Shown in the structure such as formula (I) of the quinoline nitrogen oxygen class compound:
In formula (I)~(III), R1Independently selected from H, C1~C5Alkyl, C1~C5Alkoxy or halogen；
DCP represents 2,6- dichlorophenyl；
R2Independently selected from substitution or unsubstituted phenyl, the substituent group on the phenyl is selected from C1~C5Alkyl,
C1~C5Alkoxy or halogen.
In the present invention, using nitrone compound and acetylene compound as starting material, be catalyzed using Co catalysts anti-
It answers, has efficiently obtained quinoline nitrogen oxygen class compound, various substituent groups can be had on the quinoline nitrogen oxygen class compound, are had
Important application value.
Preferably, the R1Independently selected from H, methyl, F, Cl or Br.
Preferably, R2Independently selected from phenyl, 4- tolyl, 4- fluorophenyl, 4-Cl- phenyl or 4-Br- phenyl.
In the present invention, the type of Co catalysts can generate large effect to the yield of annulation, preferably, described
Co catalysts be Cp*Co(CO)I2, using the catalyst, the yield highest of reaction.
In addition, the type of additive, oxidant and organic solvent also can generate large effect to the yield of annulation,
Preferably, the additive is silver tetrafluoroborate.
Preferably, the oxidant is silver acetate.
Preferably, the organic solvent is 1,2- dichloroethanes, when using 1,2- dichloroethanes, the yield of reaction compared with
It is high.
Preferably, reaction temperature is 60~80 DEG C.
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
(1) it is used to synthesize 2 using preparation method of the invention, when 3,4- trisubstituted quinoline nitrogen oxygen class compound, raw material
It is from a wealth of sources, while can have various substituent groups on obtained product, there is important application value.
(2) contain multiple carbon-halogen bonds, Ke Yijin on 2,3, the 4- trisubstituted quinoline nitrogen oxygen class compounds that the present invention obtains
The further derivatization of row, including dehydrogenation (such as: Tetrahedron 56 (2000) 4765-4768) and various coupling reactions,
Obtain various useful products.
Specific embodiment
The present invention will be further described combined with specific embodiments below.
Nitrone (II) (0.3mmol), alkynes (III) is added in the test tube of 25ml according to the raw material proportioning of table 1
(0.2mmol), catalyst Cp*Co(CO)I2(0.02mmol), silver tetrafluoroborate (0.04mmol), silver acetate (0.4mmol) and
Organic solvent 2ml, is mixed evenly, and after completing reaction according to the reaction condition of table 2, washs, dry, and silica gel mixed sample passes through
Column chromatographic purifying obtains corresponding quinoline oxynitrides (I), and reaction process is shown below:
Table 1
Table 2
In Tables 1 and 2, T is reaction temperature, and t is the reaction time, and Me is methyl, DCP 2,6- dichlorophenyl, Cp*For
Pentamethylcyclopentadiene base, Ph are phenyl.
In the present invention, the preparation method of raw material is referred to: Wang, C.X.；Wang,D.；Yan,H.； Wang,H.；
Pan,B.；Xin,X.；Li,X.；Wu,F.；Wan, B.Angew.Chem., Int.Ed. 2014,53,11940, detailed process is such as
Under:
By nitrobenzene (1.0equiv), aldehyde (1.1equiv) and NH4Cl (1.2equiv) is dissolved in the volume of second alcohol and water
Than the in the mixed solvent for 1:1, it is cooled with an ice bath to 0 DEG C.Then zinc powder is added into mixture.Reaction mixture is warming up to room
Temperature stirs 16 hours.Obtained reaction solution filtering, then uses CH2Cl2Washing.Filtrate uses CH2Cl2(3 × 50mL) washing, it is organic
Mutually merge, salt washing, anhydrous sodium sulfate is dry, be then concentrated under reduced pressure to give thick nitrone product, by re-crystallizing in ethyl acetate or
Person crosses column and obtains pure nitrone.
The structure confirmation data of compound is prepared in Examples 1 to 8:
The quinoline oxynitrides (I-1) being prepared by embodiment 1 nuclear magnetic resonance (1H NMR and13C NMR) detection
Data are as follows:
1H NMR (CDCl3,400MHz) δ 8.93 (d, J=8.8Hz, 1H), 7.81-7.77 (m, 1H), 7.70 (d, J=
8.0Hz,1H),7.61-7.57(m,1H),7.29-7.22(m,5H),7.20–7.17(m, 2H),7.15-7.13(m,1H),
7.12-7.10(m,2H),6.98-6.97(m,3H).13C NMR (CDCl3,100MHz)δ142.2,140.8,137.1,
135.7,135.5,135.3,134.9,132.8, 130.8,130.5,130.1,129.6,129.0,128.0,127.8,
127.7,127.4,127.1,120.3. HRMS(EI-TOF)calcd for C27H17Cl2NO(M+):441.0687,found:
441.0690。
The quinoline oxynitrides (I-2) being prepared by embodiment 2 nuclear magnetic resonance (1H NMR and13C NMR) detection
Data are as follows:
1H NMR(CDCl3, 400MHz) δ 8.81 (d, J=8.8Hz, 1H), 7.62 (d, J=8.0 Hz, 1H), 7.43 (s,
1H),7.28-7.26(m,3H),7.25-7.23(m,2H),7.19–7.14(m, 3H),7.10-7.08(m,2H),6.98-
6.96(m,3H),2.46(s,3H).13C NMR(CDCl3, 100MHz)δ141.4,139.3,139.3,136.6,135.9,
135.7,135.3,135.0,132.8, 132.2,13.8,130.4,129.7,129.6,127.9,127.7,127.6,
127.3,127.1,126.2, 120.2,21.7.HRMS(EI-TOF)calcd for C28H19Cl2NO(M+):455.0844,
found:455.0846。
The quinoline oxynitrides (I-3) being prepared by embodiment 3 nuclear magnetic resonance (1H NMR and13C NMR) detection
Data are as follows:
1H NMR(CDCl3, 400MHz) and δ 8.78 (d, J=9.2Hz, 1H), 7.71 (dd, J1=8.8 Hz, J2=2.4Hz,
1H), 7.65 (d, J=2.0Hz, 1H), 7.30-7.27 (m, 3H), 7.25-7.23 (m, 2H), 7.18-7.15 (m, 3H),
7.10-7.07(m,2H),7.00-6.96(m,3H).13C NMR (CDCl3,100MHz)δ142.4,139.3,136.6,
136.1,135.6,135.2,135.0,134.9, 132.4,130.8,130.7,130.5,129.4,128.2,128.0,
127.8,127.6,127.2,126.2, 122.3.HRMS(EI-TOF)calcd for C27H16Cl3NO(M+):475.0297,
found:475.0299。
The quinoline oxynitrides (I-4) being prepared by embodiment 4 nuclear magnetic resonance (1H NMR and13C NMR) detection
Data are as follows:
1H NMR(CDCl3, 400MHz) and δ 8.78 (d, J=9.2Hz, 1H), 7.86-7.83 (m, 2H), 7.31-7.27 (m,
3H),7.30-7.27(m,3H),7.25-7.23(m,2H),7.18–7.14(m,3H), 7.09-7.07(m,2H),7.00-
6.96(m,3H).13C NMR(CDCl3,100MHz)δ142.4, 139.6,136.6,136.0,135.2,135.0,134.8,
133.4,132.4,130.9,130.7,129.4, 128.2,128.0,127.8,127.6,127.2,123.9,122.3.HRMS
(EI-TOF)calcd for C27H16BrCl2NO(M+):518.9792,found:518.9794。
The quinoline oxynitrides (I-5) being prepared by embodiment 5 nuclear magnetic resonance (1H NMR and13C NMR) detection
Data are as follows:
1H NMR(CDCl3, 400MHz) and δ 8.92 (d, J=8.8Hz, 1H), 7.83-7.79 (m, 1H), 7.68-7.63 (m,
2H),7.28-7.25(m,2H),7.20-7.14(m,3H),7.08–7.05(m,2H), 7.02-6.98(m,2H),6.73-
6.68(m,2H).13C NMR(CDCl3,100MHz)δ163.3 (JC-F=14.8Hz), 160.2 (JC-F=23.7Hz), 142.1,
140.9,136.0,134.8,134.6, 132.5,132.5,132.4,131.5,131.4,131.4,131.3,131.3,
130.8,130.3,129.6, 129.3,127.9,127.2,120.4,115.3(JC-F=21.2Hz), 114.5 (JC-F=
20.0Hz). HRMS(EI-TOF)calcd for C27H15Cl2F2NO(M+):477.0499,found:477.0501。
The quinoline oxynitrides (I-6) being prepared by embodiment 6 nuclear magnetic resonance (1H NMR and13C NMR) detection
Data are as follows:
1H NMR(CDCl3, 400MHz) and δ 8.92 (d, J=8.8Hz, 1H), 7.84-7.80 (m, 1H), 7.66-7.63 (m,
2H),7.34-7.26(m,4H),7.23–7.18(m,1H),7.14-7.09(m,2H), 7.05-6.98(m,4H).13C NMR
(CDCl3,100MHz)δ141.9,141.0,135.5,134.8, 134.2,134.1,133.9,133.8,132.3,132.1,
130.8,130.4,129.4,128.6,127.9, 127.8,127.1,120.4.HRMS(EI-TOF)calcd for
C27H15Cl4NO(M+):508.9908, found:508.9912。
The quinoline oxynitrides (I-7) being prepared by embodiment 7 nuclear magnetic resonance (1H NMR and13C NMR) detection
Data are as follows:
1H NMR(CDCl3, 400MHz) and δ 8.92 (d, J=8.8Hz, 1H), 7.85-7.81 (m, 1H), 7.64 (d, J=
3.6Hz, 2H), 7.46 (d, J=8.4Hz, 1H), 7.29-7.27 (m, 2H), 7.23-7.19 (m, 1H), 7.16 (d, J=
8.4Hz, 2H), 7.06 (d, J=8.4Hz, 2H), 6.97 (d, J=8.4Hz, 2H)13C NMR(CDCl3,100MHz)δ
141.9,140.9,135.7,134.8,134.3,134.2, 134.1,132.3,132.2,131.5,131.1,130.9,
130.7,130.5,129.4,129.3,128.0, 127.1,122.4,122.2,120.5.HRMS(EI-TOF)calcd for
C27H15Br2Cl2NO(M+): 596.8897,found:596.8899。
The quinoline oxynitrides (I-8) being prepared by embodiment 8 nuclear magnetic resonance (1H NMR and13C NMR) detection
Data are as follows:
1H NMR(CDCl3, 400MHz) and δ 8.91 (d, J=8.8Hz, 1H), 7.79-7.75 (m, 1H), 7.70 (d, J=
8.0Hz, 1H), 7.58 (t, J=8.0Hz, 1H), 7.25-7.23 (m, 2H), 7.17-7.13 (m, 1H), 7.11-7.05 (m,
4H), 6.97 (d, J=8.0Hz, 2H), 6.77 (d, J=7.6Hz, 2H), 2.32 (s, 3H), 2.13 (s, 3H)13C NMR
(CDCl3,100MHz)δ142.3, 140.7,137.3,137.2,136.8,135.4,134.9,133.0,132.8,132.6,
130.7,130.4, 129.9,129.8,129.4,128.8,128.7,127.9,127.7,127.5,120.3,21.3,
21.2.HRMS(EI-TOF)calcd for C29H21Cl2NO(M+):469.1000, found:469.1004。
Claims (4)
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| CN1039416A (en) * | 1988-07-12 | 1990-02-07 | 武田药品工业株式会社 | Quinoline and preparation thereof and purposes |
| CN101899003A (en) * | 2010-07-23 | 2010-12-01 | 上海应用技术学院 | A kind of quinoline derivative-N-oxide ligand and its preparation method and application |
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| CN1039416A (en) * | 1988-07-12 | 1990-02-07 | 武田药品工业株式会社 | Quinoline and preparation thereof and purposes |
| CN101899003A (en) * | 2010-07-23 | 2010-12-01 | 上海应用技术学院 | A kind of quinoline derivative-N-oxide ligand and its preparation method and application |
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| A Simple and Convenient Copper-Catalyzed Tandem Synthesis of Quinoline-2-carboxylates at Room Temperature;He Huang，等;《J. Org. Chem.》;20090702;第74卷(第15期);第5476-5480页 |
| Metal-free synthesis of highly substituted quinolines under mild conditions;Rakesh Natarajan，等;《Tetrahedron Letters》;20160524;第57卷(第27-28期);第2981-2984页 |
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