CN108409747A - A kind of synthetic method of 2- aminoquinolines and dihydrofuran class compound - Google Patents
A kind of synthetic method of 2- aminoquinolines and dihydrofuran class compound Download PDFInfo
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- CN108409747A CN108409747A CN201810171226.6A CN201810171226A CN108409747A CN 108409747 A CN108409747 A CN 108409747A CN 201810171226 A CN201810171226 A CN 201810171226A CN 108409747 A CN108409747 A CN 108409747A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
- C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
- C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
Abstract
The invention discloses a kind of 2 aminoquinoline and the synthetic methods of dihydrofuran class compound.The synthetic method is：In the reactor, o-aminophenyl high-propargyl ethanol, palladium salt catalyst, ligand and oxidant are dissolved in organic solvent, add isonitrile, be stirred to react at 80~100 DEG C, reaction solution obtains 2 aminoquinolines and dihydrofuran class compound through isolating and purifying.The method of the present invention developed o-aminophenyl high-propargyl ethanol connect with isonitrile cyclization structure it is unique can 2 aminoquinolines and dihydrofuran class compound synthetic method, and basic material o-aminophenyl high-propargyl ethanol therein can be synthesized by cheap adjacent Iodoaniline and 3 butine, 1 alcohol, have the characteristics that raw material is simple and easy to get, operation is cheap, mild condition, Atom economy are high and substrate applicability is wide.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of 2- aminoquinolines and dihydrofuran class compound
Synthetic method.
Background technology
Quino furfuran compound is widely present in natural and non-natural compound, due to including quinoline and furan simultaneously
It mutters two skeletons, therefore such compound has unique biological and pharmacoligical activities, and is therefore widely used in new function
The study on the synthesis of molecule and drug.By literature survey, presently mainly pass through intramolecular or intermolecular series connection cyclization
Obtain such product (S.J.Gharpure, Y.G.ShelkeJ.Org.Chem.2017,82,2067；W.J.Yang, H.J.Ren,
Org.Lett.2013,15,1282；R.Halim, B.L.Flynn, Org.Lett.2008,10,1967；R.Halim,
B.L.Flynn, J.Org.Chem.2013,78,4708；C.Zhu, S.M.Ma, Angew.Chem.Int.Ed.2014,53,
13532；H.R.Park, E.K.Yum, Bull.Korean Chem.Soc.2016,37,958).Generally speaking, it is reported at present
Although synthetic method in terms of synthetic method progress it is very big, which part reaction needs previously prepared quinoline, or uses
For the azide compounds of explosive as raw material, operation is relatively complicated.In view of furoquinoline skeleton is ground in natural products
Study carefully the great function with medicine bioengineering application field, the synthetic method for developing more convenient and efficients is very necessary.
The one-step synthesis of polycyclic skeleton class compound is a great problem in Synthetic Organic Chemistry and drug research always,
Always research hotspot field.Utilized the high-efficiency and economic of cascade reaction, numerous complicated molecule can be from simply easily in recent years
Raw material be obtained by the reaction (L.-Q.Lu, W.-J.Xiao, Accounts of Chemical Research, 2012,45,
1278).The realization of cascade reaction realizes a step structure of polycyclic skeleton firstly the need of the suitable substrate of selection by conditional filtering
It builds.Without isolating and purifying in reaction process, therefore the efficiency of reaction can be promoted, while so that it is had certain industry and opening
Hair foreground, but the design of substrate, condition are groped, and orderly efficient combined serial is still to have under different component same system
Certain difficulty.
Therefore, development efficiently synthesizes quino furfuran compound with non-using series connection cyclization in a mild condition
Often important meaning.
Invention content
It is an object of the invention in view of the shortcomings of the prior art and insufficient, a kind of 2- aminoquinolines and dihydro furan are provided
The synthetic method of class of muttering compound.This method is using high-propargyl ethanol and isonitrile simple and easy to get as raw material, and with common
Palladium salt is oxidant as catalyst, mild mantoquita, constructs polysubstituted quino dihydrofuran compound, has atom
The features such as economy height, mild condition, wide operation cheap safety and substrate applicability, has good in actual production and research
Application prospect.
The purpose of the present invention is achieved through the following technical solutions.
The synthetic method of a kind of 2- aminoquinolines and dihydrofuran class compound, includes the following steps：
In the reactor, o-aminophenyl high-propargyl ethanol, palladium salt catalyst, ligand and oxidant are dissolved in organic solvent
In, isonitrile is added, is stirred to react at 80~100 DEG C, reaction solution obtains the 2- aminoquinolines and dihydro through isolating and purifying
Furfuran compound.
Further, the chemical equation of building-up process is as follows：
In formula, R1For benzene ring substituents, R1Selected from including 4- methyl, 4- bromines, 4- methoxyl groups, 4- ester groups, 5- chlorine, 5- first
Base, 5- trifluoromethyls, 5- bromines, 6- fluorine, 3,5- dimethyl, 3,5- dichloros, 4,6- dimethyl and 4, one or more of 6- dichloros,
Wherein, position of the digital representation group on phenyl ring before group；
R2Selected from including hydrogen or ethyl；
R3Selected from including tertiary butyl, cyclohexyl, adamantyl or 1, Isosorbide-5-Nitrae, 4- tetramethyl butyls.
Further, the palladium salt catalyst is tetra-triphenylphosphine palladium, the addition and o-aminophenyl of palladium salt catalyst
The molar ratio of high-propargyl ethanol is 0.05~0.1: 1.
Further, the ligand is 1,3- bis- (diphenylphosphine) propane, addition and the high alkynes of o-aminophenyl of ligand
The molar ratio of propyl alcohol is 0.05~0.2: 1.
Further, the oxidant is copper acetate, the addition of oxidant and rubbing for o-aminophenyl high-propargyl ethanol
You are than being 1.0~2.0: 1, preferably 1.5~2.0: 1.
Further, the solvent be acetonitrile and toluene by volume 1: 1 mixed solvent.
Further, the time being stirred to react is 3~9 hours, preferably 6~9 hours.
Further, the operation isolated and purified is：Reaction solution is extracted with ethyl acetate 3 times, merges organic phase, makes
It is dried with anhydrous magnesium sulfate, filters, remove organic solvent under reduced pressure, obtain crude product, purified through column chromatography, obtain the 2- amino quinoline
Quinoline and dihydrofuran class compound.
Further, the eluent of the column chromatography be petroleum ether and ethyl acetate by volume 20~30: 1 mixing
Solvent, preferably petroleum ether and ethyl acetate by volume 25~30: 1 mixed solvent.
The reaction principle of synthetic method of the present invention is urged in palladium salt using o-aminophenyl high-propargyl ethanol and isonitrile as raw material
Under agent and the collective effect of oxidant, reaction is started by the oxygen palladiumization of intramolecular, isonitrile migration is inserted into, the alkyl carbon of generation
Palladium key is captured by another nucleopilic reagent amino of intramolecular, is eliminated through reduction, one-step synthesis 2- aminoquinolines and dihydrofuran class
Close object.
Compared with prior art, the invention has the advantages that and advantageous effect：
(1) present invention developed o-aminophenyl high-propargyl ethanol connect with isonitrile cyclization structure it is unique
The 2- aminoquinolines of energy and the synthetic method of dihydrofuran class compound, and basic material o-aminophenyl high-propargyl therein
Alcohol can be synthesized by cheap adjacent Iodoaniline and 3- butyne-1-ols, have that raw material is simple and easy to get, operation is cheap, mild condition, original
The feature that subeconomy is high and substrate applicability is wide；
(2) synthetic method novel and high-efficiency of the present invention, it is good to the tolerance of functional group, thus be expected to be applied to actual industrial life
Production and further derivatization.
Description of the drawings
Fig. 1 and Fig. 2 is the hydrogen spectrogram and carbon spectrogram of 1 gained target product of embodiment respectively；
Fig. 3 and Fig. 4 is the hydrogen spectrogram and carbon spectrogram of 2 gained target product of embodiment respectively；
Fig. 5 and Fig. 6 is the hydrogen spectrogram and carbon spectrogram of 3 gained target product of embodiment respectively；
Fig. 7 and Fig. 8 is the hydrogen spectrogram and carbon spectrogram of 4 gained target product of embodiment respectively；
Fig. 9 and Figure 10 is the hydrogen spectrogram and carbon spectrogram of 5 gained target product of embodiment respectively；
Figure 11 and Figure 12 is the hydrogen spectrogram and carbon spectrogram of 6 gained target product of embodiment respectively；
Figure 13 and Figure 14 is the hydrogen spectrogram and carbon spectrogram of 7 gained target product of embodiment respectively；
Figure 15 and Figure 16 is the hydrogen spectrogram and carbon spectrogram of 8 gained target product of embodiment respectively；
Figure 17 and Figure 18 is the hydrogen spectrogram and carbon spectrogram of 9 gained target product of embodiment respectively；
Figure 19 and Figure 20 is the hydrogen spectrogram and carbon spectrogram of 10 gained target product of embodiment respectively；
Figure 21 and Figure 22 is the hydrogen spectrogram and carbon spectrogram of 11 gained target product of embodiment respectively；
Figure 23 and Figure 24 is the hydrogen spectrogram and carbon spectrogram of 12 gained target product of embodiment respectively；
Figure 25 and Figure 26 is the hydrogen spectrogram and carbon spectrogram of 13 gained target product of embodiment respectively；
Figure 27 and Figure 28 is the hydrogen spectrogram and carbon spectrogram of 14 gained target product of embodiment respectively.
Specific implementation mode
Technical scheme of the present invention is described in further detail below in conjunction with specific embodiment and attached drawing, but the present invention
Protection domain and embodiment it is without being limited thereto.
Embodiment 1
It is added in reaction tube 0.2 mM of N-4- (2- aminophenyls) butyl- 3- alkynes -1- alcohol, 0.02 mM of four triphen
Base phosphine palladium, 0.4 mM of Salicylaldoxime, 0.04 mM of (diphenylphosphine) propane of 1,3- bis- and 2 milliliters of acetonitriles: toluene (1:
1, v/v) mixed solvent is eventually adding 0.3 mM of tert-butyl isonitrile, and it is small under rotating speed 700rpm to be stirred to react 9 at 100 DEG C
When；Stop stirring, 5mL water is added, is extracted with ethyl acetate 3 times, merge organic phase and is dried using 0.5g anhydrous magnesium sulfates, mistake
Filter is concentrated under reduced pressure, then by column chromatographic isolation and purification, and column chromatography eluent used is the petroleum ether of volume ratio 30: 1: acetic acid
Acetate mixed solvent obtains target product, yield 68%.
Hydrogen spectrogram and carbon the spectrogram difference of gained target product are as depicted in figs. 1 and 2, and structural characterization data are as follows：
1H NMR (400MHz, CDCl3) δ 7.72 (d, J=8.4Hz, 2H), 7.48 (t, J=7.8Hz, 1H), 7.16 (t, J
=7.6Hz, 1H), 4.80 (t, J=9.0Hz, 2H), 4.01 (s, 1H), 3.05 (t, J=9.0Hz, 2H), 1.60 (s, 9H)；
13C NMR (101MHz, CDCl3) δ 162.6,154.2,149.1,128.9,126.7,121.0,113.6,
103.6,72.3,51.8,29.5,27.8；
IR(KBr)vmax3440,3055,2957,1573,1231,1076,918,751,629,549cm-1；
HRMS(ESI)Calcd for C15H19N2O[M+H]+：243.1492 Found 243.1494..
Infer that the structure of target product is as follows through data above：
Embodiment 2
Be added in reaction tube 0.2 mM of N-4- (2- amino -5- chlorphenyls) butyl- 3- alkynes -1- alcohol, 0.02 mM four
Triphenylphosphine palladium, 0.04 mM of 1,3- bis- (diphenylphosphine) propane, 0.4 mM of Salicylaldoxime and 2 milliliters of acetonitriles: toluene
The mixed solvent of (1: 1, v/v) is eventually adding 0.3 mM of tert-butyl isonitrile, is stirred to react under rotating speed 700rpm at 100 DEG C
9 hours；Stop stirring, 5mL water is added, is extracted with ethyl acetate 3 times, merge organic phase and uses 0.5g anhydrous magnesium sulfates dry
It is dry, it filters, is concentrated under reduced pressure, then by column chromatographic isolation and purification, column chromatography eluent used is the oil that volume ratio is 30: 1
Ether: ethyl acetate mixed solvent obtains target product, yield 49%.
Hydrogen spectrogram and carbon the spectrogram difference of gained target product are as shown in Figure 3 and Figure 4, and structural characterization data are as follows：
1H NMR (400MHz, CDCl3) δ 7.70 (d, J=1.8Hz, 1H), 7.61 (d, J=8.6Hz, 1H), 7.08 (dd, J
=8.6,1.9Hz, 1H), 4.79 (t, J=9.0Hz, 2H), 4.07 (s, 1H), 3.03 (t, J=9.0Hz, 2H), 1.57 (s,
9H)；
13C NMR (101MHz, CDCl3) δ 162.5,154.8,149.7,134.6,125.7,122.3,121.6,112.0,
103.7,72.4,51.9,29.5,27.4；
IR(KBr)vmax3437,2956,1639,1579,1510,1433,1385,1216,1078,918,741,637,
537cm-1；
HRMS(ESI)Calcd for C15H18ClN2O[M+H]+：277.1102, Found：277.1104.
Infer that the structure of target product is as follows through data above：
Embodiment 3
Be added in reaction tube 0.2 mM of N-4- (2- amino -4- bromophenyls) butyl- 3- alkynes -1- alcohol, 0.02 mM four
Triphenylphosphine palladium, 0.4 mM of Salicylaldoxime, 0.04 mM of (diphenylphosphine) propane of 1,3- bis- and 2 milliliters of acetonitriles: toluene
The mixed solvent of (1: 1, v/v) is eventually adding 0.3 mM of tert-butyl isonitrile, is stirred to react under rotating speed 700rpm at 100 DEG C
9 hours；Stop stirring, 5mL water is added, is extracted with ethyl acetate 3 times, merge organic phase and uses 0.5g anhydrous magnesium sulfates dry
It is dry, it filters, is concentrated under reduced pressure, then by column chromatographic isolation and purification, column chromatography eluent used is the oil that volume ratio is 25: 1
Ether: ethyl acetate mixed solvent obtains target product, yield 58%.
Hydrogen spectrogram and carbon the spectrogram difference of gained target product are as shown in Figure 5 and Figure 6, and structural characterization data are as follows：
1H NMR (400MHz, CDCl3) δ 7.79 (s, 1H), 7.45 (d, J=8.5Hz, 1H), 7.13 (d, J=8.6Hz,
1H), 4.70 (t, J=9.0Hz, 2H), 3.99 (s, 1H), 2.93 (t, J=9.0Hz, 2H), 1.47 (s, 9H)；
13C NMR (101MHz, CDCl3) δ 162.6,154.7,149.9,128.9,124.2,123.0,122.4,112.3,
103.9,72.4,51.9,29.5,27.4；
IR(KBr)vmax3427,2953,1634,1520,1429,1224,1145,1079,1017,915,826,749,
645,454cm-1；
HRMS(ESI)Calcd for C15H18BrN2O[M+H]+：321.0597 Found 321.0600.
Infer that the structure of target product is as follows through data above：
Embodiment 4
It is added in reaction tube 0.2 mM of N-4- (2- amino-4-methoxyls phenyl) butyl- 3- alkynes -1- alcohol, 0.02 mmoles
That tetra-triphenylphosphine palladium, 0.04 mM of 1,3- bis- (diphenylphosphine) propane, 0.4 mM of Salicylaldoxime and 2 milliliters of acetonitriles:
The mixed solvent of toluene (1: 1, v/v) is eventually adding 0.3 mM of tert-butyl isonitrile, is stirred under rotating speed 700rpm at 100 DEG C
Reaction 9 hours；Stop stirring, 5mL water is added, is extracted with ethyl acetate 3 times, merge organic phase and uses 0.5g anhydrous magnesium sulfates
It is dry, it filters, is concentrated under reduced pressure, then by column chromatographic isolation and purification, column chromatography eluent used is the stone that volume ratio is 30: 1
Oily ether: ethyl acetate mixed solvent obtains target product, yield 61%.
Hydrogen spectrogram and carbon the spectrogram difference of gained target product are as shown in Figure 7 and Figure 8, and structural characterization data are as follows：
1H NMR (400MHz, CDCl3) δ 7.49 (d, J=8.8Hz, 1H), 7.00 (s, 1H), 6.70 (d, J=8.8Hz,
1H), 4.64 (t, J=8.9Hz, 2H), 3.80 (s, 3H), 2.89 (t, J=8.9Hz, 2H), 1.48 (s, 9H)；
13C NMR (101MHz, CDCl3) δ 162.8,160.7,154.7,150.9,122.1,112.9,108.0,106.3,
101.4,72.3,55.2,51.8,29.6,27.3；
IR(KBr)vmax3438,2950,1637,1578,1508,1433,1382,1211,1004,914,740,509cm-1；
HRMS(ESI)Calcd for C16H20N2NaO2[M+Na]+：295.1417, Found：295.1414.
Infer that the structure of target product is as follows through data above：
Embodiment 5
Be added in reaction tube 0.2 mM of N-4- (2- amino -4- ester groups phenyl) butyl- 3- alkynes -1- alcohol, 0.02 mM
Tetra-triphenylphosphine palladium, 0.4 mM of Salicylaldoxime, 0.04 mM of (diphenylphosphine) propane of 1,3- bis- and 2 milliliters of acetonitriles: first
The mixed solvent of benzene (1: 1, v/v) is eventually adding 0.3 mM of tert-butyl isonitrile, is stirred instead under rotating speed 700rpm at 100 DEG C
It answers 9 hours；Stop stirring, 5mL water is added, is extracted with ethyl acetate 3 times, merge organic phase and uses 0.5g anhydrous magnesium sulfates dry
It is dry, it filters, is concentrated under reduced pressure, then by column chromatographic isolation and purification, column chromatography eluent used is the oil that volume ratio is 30: 1
Ether: ethyl acetate mixed solvent obtains target product, yield 56%.
Hydrogen spectrogram and carbon the spectrogram difference of gained target product are as shown in Figure 9 and Figure 10, and structural characterization data are as follows：
1H NMR (400MHz, CDCl3) δ 8.39 (s, 1H), 7.73 (d, J=2.6Hz, 1H), 4.78 (t, J=9.0Hz,
2H), 3.94 (s, 1H), 3.03 (t, J=9.0Hz, 2H), 1.57 (s, 9H)；
13C NMR (101MHz, CDCl3) δ 167.6,162.3,154.6,130.2,129.0,121.3,120.7,116.3,
105.7,72.4,52.0,51.9,29.4,27.5；
IR(KBr)vmax3406,2949,1715,1634,1519,1424,1233,1087,989,912,746,547,
461cm-1；
HRMS(ESI)Calcd for C17H21N2O3[M+H]+：301.1547 Found 301.1551..
Infer that the structure of target product is as follows through data above：
Embodiment 6
Be added in reaction tube 0.2 mM of N-4- (2- amino -5- chlorphenyls) butyl- 3- alkynes -1- alcohol, 0.02 mM four
Triphenylphosphine palladium, 0.4 mM of Salicylaldoxime, 0.04 mM of (diphenylphosphine) propane of 1,3- bis- and 2 milliliters of acetonitriles: toluene
The mixed solvent of (1: 1, v/v) is eventually adding 0.3 mM of tert-butyl isonitrile, is stirred to react under rotating speed 700rpm at 100 DEG C
9 hours；Stop stirring, 5mL water is added, is extracted with ethyl acetate 3 times, merge organic phase and uses 0.5g anhydrous magnesium sulfates dry
It is dry, it filters, is concentrated under reduced pressure, then by column chromatographic isolation and purification, column chromatography eluent used is the oil that volume ratio is 30: 1
Ether: ethyl acetate mixed solvent obtains target product, yield 74%.
The hydrogen spectrogram and carbon spectrogram of gained target product are distinguished as is illustrated by figs. 11 and 12, the following institute of structural characterization data
Show：
1H NMR (400MHz, CDCl3) δ 7.69 (d, J=1.7Hz, 1H), 7.61 (d, J=8.6Hz, 1H), 7.08 (dd, J
=8.6,1.9Hz, 1H), 4.80 (t, J=9.0Hz, 2H), 4.06 (s, 1H), 3.04 (t, J=9.0Hz, 2H), 1.56 (s,
9H)；
13C NMR (101MHz, CDCl3) δ 162.6,154.8,149.7,134.7,125.8,122.3,121.6,112.0,
103.7,72.4,51.9,29.5,27.4；
IR(KBr)vmax3439,2928,1639,1511,1436,1385,1217,1008,919,868,749,639cm-1；
HRMS(ESI)Calcd for C15H18ClN2O, [M+H]+：277.1102 Found 277.1105.
Infer that the structure of target product is as follows through data above：
Embodiment 7
Be added in reaction tube 0.2 mM of N-4- (2- amino -5- aminomethyl phenyls) butyl- 3- alkynes -1- alcohol, 0.02 mM
Tetra-triphenylphosphine palladium, 0.4 mM of Salicylaldoxime, 0.04 mM of (diphenylphosphine) propane of 1,3- bis- and 2 milliliters of acetonitriles: first
The mixed solvent of benzene (1: 1, v/v) is eventually adding 0.3 mM of tert-butyl isonitrile, is stirred instead under rotating speed 700rpm at 100 DEG C
It answers 9 hours；Stop stirring, 5mL water is added, is extracted with ethyl acetate 3 times, merge organic phase and uses 0.5g anhydrous magnesium sulfates dry
It is dry, it filters, is concentrated under reduced pressure, then by column chromatographic isolation and purification, column chromatography eluent used is the oil that volume ratio is 25: 1
Ether: ethyl acetate mixed solvent obtains target product, yield 52%.
The hydrogen spectrogram and carbon spectrogram of gained target product distinguish as shown in Figure 13 and Figure 14, the following institute of structural characterization data
Show：
1H NMR (400MHz, CDCl3) δ 7.61 (d, J=8.6Hz, 1H), 7.49 (s, 1H), 7.41-7.04 (m, 1H),
(4.78 t, J=9.0Hz, 2H), 3.94 (s, 1H), 3.05 (t, J=8.9Hz, 2H), 2.43 (s, 3H), 1.58 (s, 9H)；
13C NMR (101MHz, CDCl3) δ 167.3,163.4,155.6,151.6,128.9,126.5,124.6,122.2,
112.8,104.0,72.5,52.1,51.8,29.5,27.3；
IR(KBr)vmax3439,2920,1637,1511,1413,1257,1080,935,818,742,549cm-1；
HRMS(ESI)Calcd for C16H21N2O[M+H]+：257.1648 Found 257.1649.
Infer that the structure of target product is as follows through data above：
Embodiment 8
It is added in reaction tube 0.2 mM of N-4- (2- amino -5- trifluoromethyls) butyl- 3- alkynes -1- alcohol, 0.02 milli
Mole tetra-triphenylphosphine palladium, 0.4 mM of Salicylaldoxime, 0.04 mM of (diphenylphosphine) propane of 1,3- bis- and 2 milliliters of second
Nitrile: the mixed solvent of toluene (1: 1, v/v) is eventually adding 0.3 mM of tert-butyl isonitrile, at 100 DEG C under rotating speed 700rpm
It is stirred to react 9 hours, stops stirring.5mL water is added, is extracted with ethyl acetate 3 times, merge organic phase and uses the anhydrous sulphur of 0.5g
Sour magnesium drying, filters, is concentrated under reduced pressure, then by column chromatographic isolation and purification, it is 30: 1 that column chromatography eluent used, which is volume ratio,
Petroleum ether: ethyl acetate mixed solvent obtains target product, yield 54%.
The hydrogen spectrogram and carbon spectrogram of gained target product distinguish as shown in Figure 15 and Figure 16, the following institute of structural characterization data
Show：
1H NMR (400MHz, CDCl3) δ 8.00 (s, 1H), 7.74 (d, J=8.7Hz, 1H), 7.62 (d, J=8.7Hz,
1H), 4.84 (t, J=9.0Hz, 2H), 4.19 (s, 1H), 3.08 (t, J=8.9Hz, 2H), 1.58 (s, 9H)；
13C NMR (100MHz, DMSO) δ 152.9,128.9 (q, J=3.8Hz), 126.6,126.1 (d, J=3.6Hz),
123.9,116.0 (q, J=32.3Hz), 113.6,106.7,95.0,77.2,60.2,29.5,24.1；
IR(KBr)vmax3469,2925,2858,1638,1487,1172,1094,940,830,736,543cm-1；
HRMS(ESI)Calcd for C16H18F3N2O[M+H]+：311.1366 Found 311.1370.
Infer that the structure of target product is as follows through data above：
Embodiment 9
It is added in reaction tube 0.2 mM of N-4- (2- amino -3,5- 3,5-dimethylphenyl) butyl- 3- alkynes -1- alcohol, 0.02 milli
Mole tetra-triphenylphosphine palladium, 0.4 mM of Salicylaldoxime, 0.04 mM of (diphenylphosphine) propane of 1,3- bis- and 2 milliliters of second
Nitrile: the mixed solvent of toluene (1: 1, v/v) is eventually adding 0.3 mM of tert-butyl isonitrile, at 100 DEG C under rotating speed 700rpm
It is stirred to react 9 hours；Stop stirring, 5mL water is added, is extracted with ethyl acetate 3 times, merge organic phase and uses the anhydrous sulphur of 0.5g
Sour magnesium drying, filters, is concentrated under reduced pressure, then by column chromatographic isolation and purification, it is 30: 1 that column chromatography eluent used, which is volume ratio,
Petroleum ether: ethyl acetate mixed solvent obtains target product, yield 60%.
The hydrogen spectrogram and carbon spectrogram of gained target product distinguish as shown in Figure 17 and Figure 18, the following institute of structural characterization data
Show：
1H NMR (400MHz, CDCl3) δ 7.38 (s, 1H), 7.23 (s, 1H), 4.78 (t, J=8.9Hz, 2H), 3.96 (s,
1H), 3.05 (t, J=8.9Hz, 2H), 2.66 (s, 3H), 2.41 (s, 3H), 1.62 (s, 9H)；
13C NMR (101MHz, CDCl3) δ 162.7,152.5,146.4,134.2,131.2,129.9,117.8,112.9,
103.2,72.2,51.6,29.3,27.521.2,18.8；
IR(KBr)vmax3437,2960,1640,1437,1218,1112,976,851,775,623,492cm-1；
HRMS(ESI)Calcd for C17H23N2O[M+H]+：271.1805 Found 271.1808.
Infer that the structure of target product is as follows through data above：
Embodiment 10
It is added in reaction tube 0.2 mM of N-4- (2- amino -3,5- dichlorophenyl) butyl- 3- alkynes -1- alcohol, 0.02 mmoles
That tetra-triphenylphosphine palladium, 0.4 mM of Salicylaldoxime, 0.04 mM of (diphenylphosphine) propane of 1,3- bis- and 2 milliliters of acetonitriles:
The mixed solvent of toluene (1: 1, v/v) is eventually adding 0.3 mM of tert-butyl isonitrile, is stirred under rotating speed 700rpm at 100 DEG C
Reaction 9 hours；Stop stirring, 5mL water is added, is extracted with ethyl acetate 3 times, merge organic phase and uses 0.5g anhydrous magnesium sulfates
It is dry, it filters, is concentrated under reduced pressure, then by column chromatographic isolation and purification, column chromatography eluent used is the stone that volume ratio is 30: 1
Oily ether: ethyl acetate mixed solvent obtains target product, yield 66%.
The hydrogen spectrogram and carbon spectrogram of gained target product are distinguished as illustrated in figures 19 and 20, the following institute of structural characterization data
Show：
1H NMR (400MHz, CDCl3) δ 7.57 (dd, J=9.0,2.3Hz, 1H), 4.81 (t, J=9.0Hz, 2H), 4.17
(s, 1H), 3.05 (t, J=9.0Hz, 2H), 1.60 (s, 9H)；
13C NMR (101MHz, CDCl3) δ 162.3,153.9,131.8,129.3,125.1,119.3,114.8,105.1,
72.8,52.2,29.1,27.3；
IR(KBr)vmax3440,2924,1641,1589,1514,1402,1259,1212,1123,948,845,742,
504cm-1；
HRMS(ESI)Calcd for C15H17Cl2N2O[M+H]+：311.0712 Found 311.0716.
Infer that the structure of target product is as follows through data above：
Embodiment 11
Be added in reaction tube 0.2 mM of N-4- (2- aminophenyls) butyl- 3- alkynes -2- ethyl -1- alcohol, 0.02 mM
Tetra-triphenylphosphine palladium, 0.4 mM of Salicylaldoxime, 0.04 mM of (diphenylphosphine) propane of 1,3- bis- and 2 milliliters of acetonitriles: first
The mixed solvent of benzene (1: 1, v/v) is eventually adding 0.3 mM of tert-butyl isonitrile, is stirred instead under rotating speed 700rpm at 100 DEG C
It answers 9 hours；Stop stirring, 5mL water is added, is extracted with ethyl acetate 3 times, merge organic phase and uses 0.5g anhydrous magnesium sulfates dry
It is dry, it filters, is concentrated under reduced pressure, then by column chromatographic isolation and purification, column chromatography eluent used is the oil that volume ratio is 30: 1
Ether: ethyl acetate mixed solvent obtains target product, yield 65%.
The hydrogen spectrogram and carbon spectrogram of gained target product are distinguished as shown in figure 21 and figure, the following institute of structural characterization data
Show：
1H NMR (400MHz, CDCl3) δ 7.83-7.65 (m, 1H), 7.53-7.42 (m, 1H), 7.16 (t, J=7.5Hz,
1H), 4.99 (dq, J=9.5,6.7Hz, 1H), 3.99 (s, 1H), 3.12 (dd, J=14.2,9.5Hz, 1H), 2.71 (dd, J=
14.2,7.3Hz, 1H), 2.03-1.87 (m, 1H), 1.87-1.75 (m, 1H), 1.61 (s, 3H), 1.10 (t, J=7.4Hz,
3H)；
13C NMR (101MHz, CDCl3) δ 162.0,154.3,149.1,128.8,126.7,121.1,120.88,
113.6,103.2,86.2,51.8,32.6,29.6,29.2,9.4；
IR(KBr)vmax3429,3061,2956,1639,1516,1409,1227,996,908,756,638cm-1；
HRMS(ESI)Calcd for C17H22N2NaO[M+H]+：293.1624 Found 293.1622.
Infer that the structure of target product is as follows through data above：
Embodiment 12
It is added in reaction tube 0.2 mM of N-4- (2- aminophenyls) butyl- 3- alkynes -1- alcohol, 0.02 mM of four triphen
Base phosphine palladium, 0.4 mM of Salicylaldoxime, 0.04 mM of (diphenylphosphine) propane of 1,3- bis- and 2 milliliters of acetonitriles: toluene (1:
1, v/v) mixed solvent is eventually adding 0.3 mM of cyclohexyl isonitrile, and it is small under rotating speed 700rpm to be stirred to react 9 at 100 DEG C
When；Stop stirring, 5mL water is added, is extracted with ethyl acetate 3 times, merge organic phase and is dried using 0.5g anhydrous magnesium sulfates, mistake
Filter, decompression boils off solvent, then by column chromatographic isolation and purification, column chromatography eluent used is the petroleum ether that volume ratio is 30: 1
: ethyl acetate mixed solvent obtains target product, yield 54%.
The hydrogen spectrogram and carbon spectrogram of gained target product are distinguished as shown in figure 23 and figure 24, the following institute of structural characterization data
Show：
1H NMR (400MHz, CDCl3) δ 7.91-7.64 (m, 2H), 7.47 (ddd, J=8.4,7.0,1.4Hz, 1H),
7.20-7.05 (m, 1H), 4.80 (t, J=9.0Hz, 2H), 4.17 (s, 1H), 3.09 (t, J=9.0Hz, 2H), 2.14 (d, J=
12.5Hz, 2H), 1.93-1.56 (m, 3H), 1.58-1.38 (m, 2H), 1.39-1.12 (m, 4H)；
13C NMR (101MHz, CDCl3) δ 163.3,154.0,149.1,129.2,126.0,121.1,121.0,113.8,
102.9,72.5,49.2,33.9,27.4,25.8,25.0；
IR(KBr)vmax3421,2924,2853,1640,1517,1408,1258,1151,1078,995,756,645cm-1；
HRMS(ESI)Calcd for C17H21N2O[M+H]+：269.1648 Found 269.1652.
Infer that the structure of target product is as follows through data above：
Embodiment 13
It is added in reaction tube 0.2 mM of N-4- (2- aminophenyls) butyl- 3- alkynes -1- alcohol, 0.02 mM of four triphen
Base phosphine palladium, 0.4 mM of Salicylaldoxime, 0.04 mM of (diphenylphosphine) propane of 1,3- bis- and 2 milliliters of acetonitriles: toluene (1:
1, v/v) mixed solvent is eventually adding 0.3 mM of adamantyl isonitrile, 9 is stirred to react under rotating speed 700rpm at 100 DEG C
Hour；Stop stirring, 5mL water be added, is extracted with ethyl acetate 3 times, merge organic phase and is dried using 0.5g anhydrous magnesium sulfates,
Filtering, decompression boils off solvent, then by column chromatographic isolation and purification, column chromatography eluent used is the oil that volume ratio is 25: 1
Ether: ethyl acetate mixed solvent obtains target product, yield 62%.
The hydrogen spectrogram and carbon spectrogram of gained target product are distinguished as illustrated in figs. 25 and 26, the following institute of structural characterization data
Show：
1H NMR (400MHz, CDCl3) δ 7.69 (dd, J=7.5,4.5Hz, 1H), 7.46 (t, J=7.4Hz, 1H),
7.13 (t, J=7.4Hz, 1H), 4.80 (t, J=9.0Hz, 1H), 3.90 (s, 1H), 3.05 (t, J=8.9Hz, 2H), 2.28
(s, 6H), 2.15 (s, 3H), 1.76 (q, J=12.2Hz, 6H)；
13C NMR (101MHz, CDCl3) δ 162.7,154.2,149.1,128.9,126.6,121.0,113.6,103.5,
72.3,52.4,42.5,36.7,29.8,27.5；
IR(KBr)vmax3414,2904,1636,1511,1404,1264,1150,1079,992,919,743,640,
541,457cm-1；
HRMS(ESI)Calcd for C21H25N2O[M+H]+：321.1961 Found 321.1968.
Infer that the structure of target product is as follows through data above：
Embodiment 14
It is added in reaction tube 0.2 mM of N-4- (2- aminophenyls) butyl- 3- alkynes -1- alcohol, 0.02 mM of four triphen
Base phosphine palladium, 0.4 mM of Salicylaldoxime, 0.04 mM of (diphenylphosphine) propane of 1,3- bis- and 2 milliliters of acetonitriles: toluene (1:
1, v/v) mixed solvent, is eventually adding 0.3 mM 1, Isosorbide-5-Nitrae, 4- tetramethyl butyl isonitrile, the rotating speed 700rpm at 100 DEG C
Under be stirred to react 9 hours；Stop stirring, 5mL water is added, is extracted with ethyl acetate 3 times, merge organic phase and uses 0.5g anhydrous
Magnesium sulfate is dried, and is filtered, and is concentrated under reduced pressure, then by column chromatographic isolation and purification, it is 30 that column chromatography eluent used, which is volume ratio:
1 petroleum ether: ethyl acetate mixed solvent obtains target product, yield 73%.
The hydrogen spectrogram and carbon spectrogram of gained target product are respectively as shown in Figure 27 and Figure 28, the following institute of structural characterization data
Show：
1H NMR (400MHz, CDCl3) δ 7.72 (dd, J=8.2,2.8Hz, 2H), 7.48 (t, J=7.3Hz, 1H), 7.15
(t, J=7.4Hz, 1H), 4.80 (t, J=9.0Hz, 2H), 4.07 (s, 1H), 3.04 (t, J=9.0Hz, 2H), 2.05 (s,
2H), 1.66 (s, 6H), 1.04 (s, 9H)；
13C NMR (101MHz, CDCl3) δ 162.5,154.1,149.2,128.8,126.7,120.9,113.6,
103.5,72.2,55.8,51.9,31.8,31.6,29.9,27.5；
IR(KBr)vmax3691,3443,2952,1642,1518,1410,1229,1150,1077,1000,931,752,
630cm-1；
HRMS(ESI)Calcd for C19H27N2O[M+H]+：299.2118 Found 299.2122.
Infer that the structure of target product is as follows through data above：
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (9)
1. the synthetic method of a kind of 2- aminoquinolines and dihydrofuran class compound, which is characterized in that include the following steps：
In the reactor, o-aminophenyl high-propargyl ethanol, palladium salt catalyst, ligand and oxidant are dissolved in organic solvent,
Isonitrile is added, is stirred to react at 80~100 DEG C, reaction solution obtains the 2- aminoquinolines and dihydro furan through isolating and purifying
Class of muttering compound.
2. synthetic method according to claim 1, which is characterized in that the following institute of chemical equation of building-up process
Show：
In formula, R1For benzene ring substituents, R1Selected from including 4- methyl, 4- bromines, 4- methoxyl groups, 4- ester groups, 5- chlorine, 5- methyl, 5-
Trifluoromethyl, 5- bromines, 6- fluorine, 3,5- dimethyl, 3,5- dichloros, 4,6- dimethyl and 4, one or more of 6- dichloros；
R2Selected from including hydrogen or ethyl；
R3Selected from including tertiary butyl, cyclohexyl, adamantyl or 1, Isosorbide-5-Nitrae, 4- tetramethyl butyls.
3. synthetic method according to claim 1 or 2, which is characterized in that the palladium salt catalyst is tetra-triphenylphosphine palladium,
The addition of palladium salt catalyst is 0.05~0.1: 1 with the molar ratio of o-aminophenyl high-propargyl ethanol.
4. synthetic method according to claim 1 or 2, which is characterized in that the ligand is 1,3- bis- (diphenylphosphine) third
Alkane, the addition of ligand are 0.05~0.2: 1 with the molar ratio of o-aminophenyl high-propargyl ethanol.
5. synthetic method according to claim 1 or 2, which is characterized in that the oxidant is copper acetate, and oxidant adds
The molar ratio for entering amount and o-aminophenyl high-propargyl ethanol is 1.5~2.0: 1.
6. synthetic method according to claim 1 or 2, which is characterized in that the organic solvent is that acetonitrile and toluene press body
Mixed solvent of the product than 1: 1.
7. synthetic method according to claim 1 or 2, which is characterized in that the time being stirred to react is 6~9 hours.
8. synthetic method according to claim 1 or 2, which is characterized in that the operation isolated and purified is：By reaction solution
It is extracted with ethyl acetate 3 times, merges organic phase, dried using anhydrous magnesium sulfate, filter, remove organic solvent under reduced pressure, obtain and slightly produce
Object is purified through column chromatography, obtains the 2- aminoquinolines and dihydrofuran class compound.
9. synthetic method according to claim 8, which is characterized in that the eluent of the column chromatography is petroleum ether and acetic acid
Ethyl ester by volume 25~30: 1 mixed solvent.
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| CN108993600A (en) * | 2018-08-30 | 2018-12-14 | 郑州大学 | Application of the bidentate phosphite ester ligand in the building reaction of C-B key |
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