CN104496875B - The synthetic method of the carboxaldehyde radicals N phenyl pyrazoline Ka Lin of 2 pi-allyl 2 - Google Patents

The synthetic method of the carboxaldehyde radicals N phenyl pyrazoline Ka Lin of 2 pi-allyl 2 Download PDF

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CN104496875B
CN104496875B CN201410766280.7A CN201410766280A CN104496875B CN 104496875 B CN104496875 B CN 104496875B CN 201410766280 A CN201410766280 A CN 201410766280A CN 104496875 B CN104496875 B CN 104496875B
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徐华栋
贾志宏
徐科
周皓
沈美华
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Chengdu Rongchuang Yiheng Biomedical Technology Co ltd
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Changzhou University
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/08—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon radicals, substituted by hetero atoms, attached to ring carbon atoms

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Abstract

The invention discloses the synthetic method of the carboxaldehyde radicals N phenyl pyrazoline Ka Lin of 2 pi-allyl 2, belong to chemical pharmacy and fine chemistry industry preparing technical field.Realize the one pot process of polysubstituted, the multiple functionalized carboxaldehyde radicals N phenyl pyrazoline Ka Lin of 2 pi-allyl 2, the sulphonyl triazole of metal catalytic has been used to resolve into metal carbene, subsequent metal carbene cyclisation, efficiently obtains the carboxaldehyde radicals N phenyl pyrazoline Ka Lin of 2 pi-allyl 2 of high added value.The present invention has wide application in chemical pharmacy and field of fine chemical efficiently to prepare the technology path that the carboxaldehyde radicals N phenyl pyrazoline Ka Lin derivatives of 2 pi-allyl of functionalization 2 provide first.

Description

The synthetic method of 2- pi-allyl -2- carboxaldehyde radicals-N- phenyl pyrazoline Ka Lin
Technical field
2- pi-allyl Bi Ka Lin 2- is prepared the invention belongs to chemical pharmacy and fine chemistry industry preparing technical field, i.e. one kettle way Formaldehyde, especially relates to the Cabbeen cyclisation rearrangement reaction of metal catalytic, efficiently generates a kind of pyrrole containing quaternary carbon of multifunctional dough Ka Lin structures.The present invention provides a technical strategies and design plan efficiently to prepare the Bi Ka Lin derivatives of functionalization Slightly, there is wide application in chemical pharmacy and field of fine chemical.
Background technology
It is the important organic compound of a major class that pyrrole, which coughs up Lin, and much the compound containing this class formation has special chemistry With bioactivity, exist in many natural products and drug molecule.And the Bi Ka Lin class compounds containing aldehyde radical and alkene phenyl The even more organic molecule of high added value, because aldehyde radical and alkene phenyl very easily can obtain many other by further derivatization The azacyclo- of structure.2- pi-allyl -2- carboxaldehyde radicals-N- phenyl pyrazoline Ka Lin is because containing a variety of functional groups in its structure, it should be one The very valuable nitrogen heterocyclic of class, the preparation method of current this kind of compound does not have no report also.
The content of the invention
The purpose of the present invention is to illustrate a kind of 2- pi-allyls -2- carboxaldehyde radicals-N- phenyl pyrazoline Ka Lin preparation methods, specifically Exactly invent a kind of efficient one kettle way and prepare 2- pi-allyl -2- carboxaldehyde radicals-N- phenyl pyrazoline Ka Lin.
To realize above-mentioned synthesis purpose, the present invention is adopted the following technical scheme that, is summarised as shown reaction equation：(formula 1).In appropriate solvent, various 1- sulfonyls triazoles 1 are cyclized under the catalysis of appropriate metallic catalyst and reset, by appropriate water 2- pi-allyl -2- carboxaldehyde radicals-N- phenyl pyrazoline Ka Lin 2 is obtained after solution processing.
R in general formula of molecular structure 1,21For various substituents (specially o-, m-, to methoxyl group, alkyl, halogen etc.)；R2 (it is specially methyl, ethyl, benzyl for various substituted aryl (being specially phenyl, p-methylphenyl etc.), various substituted alkyl Deng), various aliphatic radicals (be specially methyl esters, ethyl ester etc.), various halogens (being specially chlorine, bromine, fluorine) etc.；R3 is various alkyl, various Substituted aryl etc..
A kind of synthetic method of 2- pi-allyls -2- carboxaldehyde radicals-N- phenyl pyrazoline Ka Lin, is carried out as steps described below：
1- sulfonyls triazole 1, metallic catalyst are blended in a kind of organic solvent and stirred by a certain percentage, according to substrate And specificity of reagent, temperature control is between certain temperature, after certain time, stop reaction, add proper amount of methanol, potassium carbonate and A small amount of water, is stirred overnight.Extracted three times with organic solvent ethyl acetate or dichloromethane, organic phase uses saturated aqueous common salt after merging Wash, then with anhydrous sodium sulfate drying, remove solvent under reduced pressure, residue with Ethyl acetate and petroleum ether are eluant, eluent, silicagel column color Spectrum is isolated and purified, and obtains corresponding azacyclo- aldehyde 2.Or remove organic solvent, the direct silica gel chromatograph of residue under reduced pressure after the completion of reaction Post separation.
The structural formula of wherein described 1- sulfonyls triazole 1 isWherein R1To be each Kind of substituent (specially o-, m-, to methoxyl group, alkyl, halogen etc.)；R2(it is specially phenyl, to first for various substituted aryl Base phenyl etc.), various substituted alkyl (being specially methyl, ethyl, benzyl etc.), various aliphatic radicals (being specially methyl esters, ethyl ester etc.), Various halogens (being specially chlorine, bromine, fluorine) etc.；R3For various alkyl, various substituted aryl etc..
Wherein described solvent is that tetrahydrofuran, toluene, dichloromethane, chloroform, 1,2- dichloromethane etc. are nonpolar molten Agent.
Wherein described 1- sulfonyls triazole 1, catalyst molar ratio are 1.0：0.005 to 1.0：Between 0.05.
Wherein described catalyst is rhodium compound and the trifluoromethanesulfonic acids, trifluoro such as rhodium acetate, rhodium caprylate, isophthalic acid rhodium The silver salt such as the copper compounds such as copper acetate and silver trifluoromethanesulfonate.
Wherein described reaction temperature is between 50-120 degree.
The wherein described reaction time is between 10 minutes to 5 hours.
Advantages of the present invention
1st, the operation is easy, only needs one pot reaction just can efficiently prepare two kinds of azacyclo-s.
2nd, the product structure of the reaction is novel, outside the method for going out this patent report, temporarily without other preparation methods.
3rd, the product of the reaction is the compound of high added value.
Embodiment
The present invention is given below by example and is described further：
Following non-limiting example 1-3# or comparative example 1-2# are used for illustrating the present invention, rather than to this hair It is bright to be limited, in the protection domain of spirit and claims of the present invention, any modifications and changes made to the present invention, Belong to protection scope of the present invention.
Raw material used in the present invention, reagent and catalyst are prepared by reference to pertinent literature, solvent by purifying and It is refined.
Embodiment 1
2 mMs of 1- are blended in toluene sulfo group triazole 1k, 0.01 mM of rhodium acetate in 10 milliliters of toluene and stirred, After 120 degree, 2 hours of temperature control, stop heating, add 2 ml methanols, 5 mMs of potassium carbonate and a drop water, be stirred at room temperature 12 Hour.Extracted three times with organic solvent ethyl acetate, organic phase is washed after merging with saturated common salt, then it is dry with anhydrous sodium sulfate It is dry, remove solvent under reduced pressure, residue with Ethyl acetate and petroleum ether are eluant, eluent, and silica gel column chromatogram separating purification obtains corresponding Azacyclo- aldehyde 2a (being shown in Table 1).Or remove organic solvent, the direct silica gel chromatograph post separation of residue under reduced pressure after the completion of reaction.
Embodiment 2
2 mMs of 1- are blended in 10 milliliters of dichloroethanes and stirred to toluene sulfo group triazole 1g, 0.1 mM of rhodium acetate Mix, after 50 degree, 5 hours of temperature control, stop heating, add 2 ml methanols, 5 mMs of potassium carbonate and a drop water, be stirred at room temperature 8 hours.Extracted three times with organic solvent ethyl acetate, organic phase is washed after merging with saturated common salt, then it is dry with anhydrous sodium sulfate It is dry, remove solvent under reduced pressure, residue with Ethyl acetate and petroleum ether are eluant, eluent, and silica gel column chromatogram separating purification obtains corresponding Azacyclo- aldehyde 2g (being shown in Table 1).Or remove organic solvent, the direct silica gel chromatograph post separation of residue under reduced pressure after the completion of reaction.
Embodiment 3
2 mMs of 1- are blended in toluene sulfo group triazole 1i, 0.04 mM of rhodium acetate in 10 milliliters of toluene and stirred, After 120 degree, 10 minutes of temperature control, stop heating, add 2 ml methanols, 5 mMs of potassium carbonate and a drop water, be stirred at room temperature 12 hours.Extracted three times with organic solvent ethyl acetate, organic phase is washed after merging with saturated common salt, then it is dry with anhydrous sodium sulfate It is dry, remove solvent under reduced pressure, residue with Ethyl acetate and petroleum ether are eluant, eluent, and silica gel column chromatogram separating purification obtains corresponding Azacyclo- aldehyde 2i (being shown in Table 1).Or remove organic solvent, the direct silica gel chromatograph post separation of residue under reduced pressure after the completion of reaction.
Table 1. prepares 2- pi-allyl -2- carboxaldehyde radicals-N- phenyl pyrazoline Ka Lin
2a:Yellow oil, 66%；1H NMR(400MHz,CDCl3) δ 9.59 (s, 1H), 6.81 (d, J=8.9Hz, 2H),6.69(m,2H),5.67-5.56(m,1H),5.06(brs,1H),5.03(brs,1H),3.75(s,3H),3.60-3.46 (m, 2H), 2.87 (dd, J=14.4,6.2Hz, 1H), 2.59 (dd, J=14.3,8.4Hz, 1H), 2.19-2.00 (m, 4H)； 13C NMR(100MHz,CDCl3)δ204.1,133.3,118.8,114.9,114.4,71.9,55.8,50.9,35.1,33.9, 23.5；HRMS (ESI) m/z theoretical value for C15H19NO2Na+[M+Na]+268.1308, measured value 268.1302.
2b:Yellow oil, 64%；1H NMR(300MHz,CDCl3)δ9.59(s,1H),7.24-7.15(m,2H), 6.73 (t, J=7.3Hz, 1H), 6.60 (d, J=8.0Hz, 2H), 5.74-5.56 (m, 1H), 5.10-5.04 (m, 1H), 5.02 (m, 1H), 3.64-3.43 (m, 2H), 2.93 (dd, J=14.5,6.3Hz, 1H), 2.63 (dd, J=14.5,8.5Hz, 1H), 2.18-1.96(m,4H)；13C NMR(75MHz,CDCl3)δ204.2,145.5,133.2,129.4,118.9,117.2, 112.8,71.9,50.5,35.1,34.1,23.4；HRMS (ESI) m/z theoretical value for C14H18NO+[M+H]+216.1383, it is real Measured value 216.1375.
2c:Yellow oil, 65%；1H NMR(400MHz,CDCl3) δ 9.60 (s, 1H), 7.02 (d, J=8.3Hz, 2H), 6.54 (d, J=8.4Hz, 2H), 5.66 (ddd, J=16.7,8.5,6.5Hz, 1H), 5.08 (d, J=6.9Hz, 1H), 5.04 (brs, 1H), 3.58-3.47 (m, 2H), 2.91 (dd, J=14.4,6.2Hz, 1H), 2.62 (dd, J=14.4,8.5Hz, 1H),2.26(s,3H),2.15-1.99(m,4H)；13C NMR(100MHz,CDCl3)δ204.3,143.3,133.4,129.9, 126.4,118.7,112.9,71.8,50.5,35.1,34.3,23.4,20.3；HRMS (ESI) m/z theoretical value for C15H20NO+ [M+H]+230.1539, measured value 230.1531.
2d:Yellow oil, 68%；1H NMR(400MHz,CDCl3) δ 9.55 (s, 1H), 7.13 (d, J=9.0Hz, 2H), 6.51 (d, J=9.0Hz, 2H), 5.74-5.48 (m, 1H), 5.07 (brs, 1H), 5.04-5.02 (m, 1H), 3.60- 3.39 (m, 2H), 2.88 (dd, J=14.5,6.4Hz, 1H), 2.60 (dd, J=14.5,8.3Hz, 1H), 2.18-1.96 (m, 4H)；13C NMR(100MHz,CDCl3)δ203.3,144.1,132.8,129.1,122.2,119.2,114.0,72.0,50.8, 34.8,34.1,23.3；HRMS (ESI) m/z theoretical value for C14H17ClNO+[M+H]+250.0993, measured value 250.0985.
2e:Yellow oil, 45%；1H NMR(400MHz,CDCl3) δ 9.55 (s, 1H), 7.07 (t, J=8.1Hz, 1H), 6.69 (dd, J=7.8,1.3Hz, 1H), 6.58 (t, J=2.2Hz, 1H), 6.44 (dd, J=8.4,2.5Hz, 1H), 5.72-5.54(m,1H),5.09-5.07(m,1H),5.06-5.03(m,1H),3.60-3.51(m,1H),3.51-3.43(m, 1H), 2.90 (dd, J=14.5,6.4Hz, 1H), 2.62 (dd, J=14.5,8.4Hz, 1H), 2.16-1.98 (m, 4H)；13C NMR(100MHz,CDCl3)δ203.2,146.6,135.2,132.7,130.2,119.3,117.2,112.9,111.0,72.1, 50.7,34.9,34.2,23.2；HRMS (ESI) m/z theoretical value for C14H17ClNO+[M+H]+250.0993, measured value 250.0988.
2f:Yellow oil, 46%；1H NMR(400MHz,CDCl3)δ9.60(s,1H),7.24–7.15(m,2H), 6.73 (t, J=7.3Hz, 1H), 6.62 (d, J=8.1Hz, 2H), 5.06-4.92 (m, 1H), 3.62-3.54 (m, 1H), 3.52- 3.47 (m, 1H), 2.78 (dd, J=15.0,6.6Hz, 1H), 2.67 (dd, J=15.0,8.5Hz, 1H), 2.11-1.98 (m, 4H),1.65(s,3H),1.51(s,3H)；13CNMR(100MHz,CDCl3)δ204.4,145.4,135.0,129.4,118.5, 117.4,113.1,72.9,50.6,34.1,29.0,26.1,23.4,18.0；HRMS (ESI) m/z theoretical value for C16H22NO+ [M+H]+244.1696, measured value 244.1687.
2g:Yellow oil, 65%；1H NMR(400MHz,CDCl3)δ9.44(s,1H),7.25–7.17(m,2H), 6.74 (t, J=7.3Hz, 1H), 6.56 (d, J=8.1Hz, 2H), 5.54 (d, J=6.8Hz, 2H), 3.74-3.63 (m, 1H), 3.61-3.55 (m, 1H), 3.43 (d, J=15.1Hz, 1H), 3.11 (d, J=15.1Hz, 1H), 2.40-2.24 (m, 2H), 2.17–2.03(m,2H)；13C NMR(100MHz,CDCl3)δ203.1,145.0,129.6,128.0,122.1,117.3, 112.6,72.3,50.5,40.1,33.3,23.3；HRMS (ESI) m/z theoretical value for C14H17BrNO+[M+H]+294.0488, Measured value 294.0485.
2h:Yellow oil, 63%；1H NMR(400MHz,CDCl3) δ 9.46 (s, 1H), 6.81 (d, J=9.1Hz, 2H), 6.61 (d, J=7.1Hz, 2H), 5.26 (s, 1H), 5.09 (s, 1H), 3.75 (s, 3H), 3.67-3.59 (m, 1H), 3.55 (dd, J=15.5,7.6Hz, 1H), 3.29 (d, J=14.8Hz, 1H), 2.96 (d, J=14.9Hz, 1H), 2.40-2.21 (m, 2H),2.21-2.03(m,2H)；13C NMR(125MHz,CDCl3)δ203.3,138.1,117.3,115.1,113.8,72.0, 55.8,50.7,38.3,33.3,23.3；HRMS (ESI) m/z theoretical value for C15H19ClNO2 +[M+H]+280.1099, actual measurement Value 280.1085.
2i:Yellow oil, 64%；1H NMR(400MHz,CDCl3)δ9.55(s,0.36H),9.51(s,0.59H), 6.83–6.75(m,2H),6.71–6.66(m,2H),5.95–5.87(m,0.36H),5.64–5.47(m,0.63H),5.17– 5.03 (m, 0.76H), 4.95 (dt, J=10.6,1.5Hz, 0.64H), 4.86 (dt, J=17.4,1.5Hz, 0.63H), 3.74 (s, 3H), 3.59-3.29 (m, 3H), 2.19-1.88 (m, 4H), 1.05 (d, J=6.7Hz, 1H), 0.78 (d, J=6.9Hz, 1.14H)；13C NMR(100MHz,CDCl3)δ200.8,200.0,152.2,139.5,138.1,134.0,116.1,115.7, 115.1,114.9,114.7,114.6,73.5,55.7,51.3,51.1,36.1,34.4,30.3,30.0,23.4,23.3, 14.0,12.5；HRMS (ESI) m/z theoretical value for C16H22NO2 +[M+H]+260.1645, measured value 260.1639.

Claims (5)

1. a kind of synthetic method of 2- pi-allyls -2- formoxyls-N- phenylpyrrole quinoline derivants, it is characterised in that according to following steps It is rapid to carry out：
1- sulfonyls triazole, metal ion catalyst are blended in a kind of organic solvent and stirred by a certain percentage, according to substrate And specificity of reagent, temperature control is between certain temperature, after certain time, stops reaction, adds proper amount of methanol, potassium carbonate and few Water is measured, is stirred overnight；
Extracted three times with organic solvent ethyl acetate or dichloromethane, organic phase is washed after merging with saturated common salt, then with anhydrous Sodium sulphate is dried, and removes solvent under reduced pressure, and residue with Ethyl acetate and petroleum ether are eluant, eluent, silica gel column chromatogram separating purification, Obtain 2- pi-allyl -2- formoxyl-N- phenylpyrrole quinoline derivants；Or remove organic solvent, residue under reduced pressure after the completion of reaction Direct silica gel chromatograph post separation；
The structural formula of described 2- pi-allyl -2- formoxyl-N- phenylpyrrole quinoline derivants is64964dest_path_image001；
Described metal ion catalyst is rhodium acetate；
The structural formula of wherein described 1- sulfonyls triazole is, wherein R1For Methoxyl group, halogen；R2For methyl, chlorine, bromine, fluorine； R3For alkyl.
2. a kind of synthetic method of 2- pi-allyls -2- formoxyls-N- phenylpyrrole quinoline derivants according to claim 1, It is characterized in that the solvent is tetrahydrofuran, toluene, dichloromethane, chloroform.
3. a kind of synthetic method of 2- pi-allyls -2- formoxyls-N- phenylpyrrole quinoline derivants according to claim 1, It is characterized in that wherein described 1- sulfonyls triazole, metal ion catalyst mol ratio are 1.0：0.005 to 1.0：0.05 Between.
4. a kind of synthetic method of 2- pi-allyls -2- formoxyls-N- phenylpyrrole quinoline derivants according to claim 1, It is characterized in that wherein described reaction temperature is between 50-120 degree.
5. a kind of synthetic method of 2- pi-allyls -2- formoxyls-N- phenylpyrrole quinoline derivants according to claim 1, It is characterized in that the wherein described reaction time is between 10 minutes to 5 hours.
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