CN113200984B - Synthetic method of indole base compound - Google Patents
Synthetic method of indole base compound Download PDFInfo
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Abstract
The invention relates to the technical field of organic synthesis, in particular to a synthesis method of an indole base compound. The indole base compound shown as I is obtained by taking the compounds shown as the formula II and the formula III as raw materials and reacting in ionic liquid under the catalysis of a catalyst acetylacetone metal complex. The invention creates a synthesis method for synthesizing the indole base compounds by a one-step method, and the method has the advantages of simple operation, wide substrate adaptability and high product yield.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a synthesis method of an indole base compound.
Background
The azacyclo compound is an important organic molecule and widely exists in medicine, pesticide and material molecules, wherein the indole base compound is a core structural unit of a plurality of medicine molecules due to potential biological activity, and particularly, the indole base compound such as indoxazine has the biological activity of indoxazine and indole, so that the azacyclo compound is more widely concerned by medicinal chemists.
Synthetic methods of indolizindoles have been reported in the literature, such as the preparation of tryptamine and unsaturated lactones by Pictet-Spengler-like condensation, but these reactions require expensive gold and silver metal catalysts, and the unsaturated lactones are not readily available as starting materials. Therefore, it is very important to develop a simple method for synthesizing indolizinoindoles.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a novel synthesis method of an indole base compound, the synthesis method only needs one step to obtain a target product, and the method is simple to operate, wide in substrate adaptation and high in product yield, and is very suitable for industrialization.
In order to achieve the purpose, the invention specifically adopts the following technical scheme:
a synthetic method of indole base compounds comprises the following steps of reacting 3-indoleethylamine compounds shown in a formula II and 3-butynoic acid compounds shown in a formula III in ionic liquid under the catalysis of acetylacetone metal complexes to obtain the indole base compounds shown in the formula I:
wherein:
R 1 is hydrogen, halogen, C 1 ～C 6 Alkyl of (C) 1 ～C 4 Halogenoalkyl of, C 1 ～C 4 Alkoxy group of (a);
R 2 is hydrogen, C 1 ～C 4 Alkyl groups of (a);
R 3 is hydrogen, C 1 ～C 4 Alkyl groups of (a);
R 4 is hydrogen, C 1 ～C 6 Alkyl of (C) 3 ～C 6 Cycloalkyl, aryl, benzyl.
Preferably, said
R 1 Is hydrogen, halogen, methyl, halomethyl or methoxy;
R 2 is hydrogen or methyl;
R 3 is hydrogen, methyl or ethyl;
R 4 is hydrogen, methyl, C 3 ～C 6 Cycloalkyl, phenyl, tolyl, or benzyl.
Further preferably, the compounds of formula II, formula III and formula I in the reaction are selected from the following:
preference is given toThe ionic liquid is [ BMIm]X、[PMIm]X、[HMIm]X、[BMMIm]X、[BMMIm]BF 4 、[EMIm]BF 4 Wherein X is halogen.
Preferably, the metal in the catalyst acetylacetone metal complex is selected from 2-valent metal ions.
Further preferably, the metal in the catalyst acetylacetone metal complex is selected from Ni 2+ 、Cu 2+ 、Co 2+ Or Vo 2+ 。
Preferably, the reaction temperature is 50-80 ℃.
Preferably, the amount of the catalyst is 3-8% of the amount of the compound substance shown in the formula II.
Preferably, after the reaction is completed, post-treatment is performed, and the post-treatment comprises the following steps:
(1) adding saturated sodium carbonate solution into the reaction solution after the reaction is finished, and continuously stirring for reaction;
(2) adding ethyl acetate into the system for 2-5 times, and combining organic layers;
(3) the organic layer obtained in step (2) was washed with brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure.
Further preferably, the recrystallization is carried out using 95% ethanol as a solvent subsequent to the step (3).
Advantageous effects
(1) The invention creates a new synthetic method for synthesizing indole base compounds by a one-step method;
(2) the method has the advantages of simple operation, wide substrate adaptability and high product yield.
Detailed Description
The following will clearly and completely describe the technical solutions in the specific embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Wherein the terms in the present specification have the following meanings:
C 1 ～C 6 the alkyl group of (b) means a straight or branched alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, isopentyl, hexyl, isohexyl, etc.;
C 1 ～C 4 the alkyl group of (b) means a straight or branched alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl and the like.
Halogen means a fluorine, chlorine, bromine or iodine atom;
C 1 ～C 4 the haloalkyl group of (a) means a straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms substituted with a halogen atom, such as a chloromethyl group, a bromomethyl group, a fluoromethyl group, an iodomethyl group, a 1-chloroethyl group, a 2-chloroethyl group, a 1-bromoethyl group, a 1-chloropropyl group, a 1-bromoisopropyl group, a 2-chloro-n-butyl group and the like;
C 3 ～C 6 the cycloalkyl group of (b) means a cycloalkyl group having 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like;
C 1 ～C 4 the alkoxy group of (b) means a straight or branched alkoxy group having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and the like;
aryl refers to the generic term for monovalent radicals remaining after removal of a hydrogen atom from an aromatic core carbon of an aromatic hydrocarbon molecule, which include phenyl, naphthyl, or other substituted aryl radicals such as tolyl, ethylphenyl, n-propylphenyl, and the like.
The present invention will be described in detail with reference to examples below to facilitate understanding of the present invention by those skilled in the art.
Example 1
The reaction formula is as follows:
a reaction flask was charged with 10mmol of the compound of formula IIa, 12mmol of the compound of formula IIIa and 10mL of ionic liquid [ BMIm ]]Br, stirred until dissolved, then 0.5mmol of the catalyst Cu (acac) 2 Continuously stirring for about 0.5h, heating to 70 ℃, keeping the temperature, stirring for reaction, detecting the reaction process by using a thin-layer chromatography, cooling to room temperature after the reaction is finished, adding 60mL of saturated sodium carbonate solution, and stirring for reaction for 0.5 h; adding 20mL of ethyl acetate into the reaction system for three times respectively, combining organic layers, washing the organic layers twice with saturated salt water, combining the organic layers, drying with anhydrous sodium sulfate, evaporating the solvent under reduced pressure to obtain a solid, and recrystallizing by using 95% ethanol as a solvent to obtain the compound of the formula Ia as a white solid with the yield: 94 percent. ESI-LRMS M/z 255.2[ M + H ]] + , 1 H NMR(500MHz,DMSO-d6)δ:1.59(s,3H),2.05-2.32(m,4H),2.39(s,3H),2.68-2.71(m,2H),3.41-3.52(m,2H),6.68(dd,J＝8.7,2.4Hz,1H),6.81(d,J＝2.4Hz,1H),7.11(d,J＝8.7Hz,1H),10.56(s,1H)。
Example 2
The reaction formula is as follows:
a reaction flask was charged with 10mmol of the compound of formula IIb, 12mmol of the compound of formula IIIb and 10mL of ionic liquid [ PMIm]Cl, stirred until dissolved, then 0.4mmol of the catalyst vo (acac) 2 Continuously stirring for about 0.5h, heating to 50 ℃, preserving heat and stirringDetecting the reaction process by using thin-layer chromatography, cooling to room temperature after the reaction is finished, adding 60mL of saturated sodium carbonate solution, and stirring for reacting for 0.5 h; adding 20mL of ethyl acetate into the reaction system for three times respectively, combining organic layers, washing the organic layers twice with saturated saline solution, combining the organic layers, drying with anhydrous sodium sulfate, evaporating the solvent under reduced pressure to obtain a solid, and recrystallizing with 95% ethanol as a solvent to obtain the compound shown in the formula Ib as a yellow solid with the yield: and 69 percent. ESI-LRMS M/z:289.7[ M + H ]] + , 1 H NMR(500MHz,DMSO-d6)δ:1.33(s,3H),2.11-2.38(m,4H),2.55-2.79(m,2H),3.62(s,3H),4.07-4.23(m,1H),4.59-4.73(m,1H),6.39(dd,J＝8.9,2.6Hz,1H),6.61(d,J＝2.6Hz,1H),7.29(d,J＝8.9Hz,1H)。
Example 3
The reaction formula is as follows:
a reaction flask was charged with 10mmol of the compound of formula IIc above, 12mmol of the compound of formula IIIc and 10mL of ionic liquid [ HMim]Br, dissolved by stirring, and then 0.8mmol of catalyst Cu (acac) 2 Continuously stirring for about 0.5h, heating to 75 ℃, keeping the temperature, stirring for reaction, detecting the reaction process by using thin-layer chromatography, cooling to room temperature after the reaction is finished, adding 60mL of saturated sodium carbonate solution, and stirring for reaction for 0.5 h; adding 20mL of ethyl acetate into the reaction system for three times respectively, combining organic layers, washing the organic layers twice with saturated saline, combining the organic layers, drying with anhydrous sodium sulfate, evaporating the solvent under reduced pressure to obtain a solid, and recrystallizing with 95% ethanol as a solvent to obtain the compound of the formula Ic, wherein the compound is a yellow solid, and the yield is as follows: 74 percent.
ESI-LRMS m/z:389.1[M+H] + , 1 H NMR(500MHz,DMSO-d6)δ:0.96(t,3H),1.51-1.63(m,2H),2.18-2.29(m,2H),2.37(s,3H),2.51-2.67(m,2H),2.69-2.78(m,2H),3.62(s,3H),3.78(s,3H),3.91-4.02(m,1H),6.38(dd,J＝8.2,2.1Hz,1H),6.82(d,J＝2.1Hz,1H),6.85(d,J＝8.2Hz,1H),7.02(d,J＝7.8Hz,2H),7.02(d,J＝6.8Hz,2H)。
Example 4
The reaction formula is as follows:
a reaction flask was charged with 10mmol of the compound of formula IIa, 12mmol of the compound of formula IIIa and 10mL of ionic liquid [ BMMIm ]]Br, dissolved by stirring, and then 0.6mmol of catalyst Ni (acac) 2 Continuously stirring for about 0.5h, heating to 80 ℃, then keeping the temperature and stirring for reaction, detecting the reaction process by using a thin-layer chromatography, cooling to room temperature after the reaction is finished, adding 60mL of saturated sodium carbonate solution, and stirring for reaction for 0.5 h; adding 20mL of ethyl acetate into the reaction system for three times respectively, combining organic layers, washing the organic layers twice with saturated salt water, combining the organic layers, drying with anhydrous sodium sulfate, evaporating the solvent under reduced pressure to obtain a solid, and recrystallizing by using 95% ethanol as a solvent to obtain the compound of the formula Ia as a white solid with the yield: 74 percent.
Example 5
The reaction formula is as follows:
a reaction flask was charged with 10mmol of the compound of formula IIe above, 12mmol of the compound of formula IIIe and 10mL of ionic liquid [ BMim ]]Br, dissolved by stirring, and then 0.4mmol of catalyst Cu (acac) 2 Continuously stirring for about 0.5h, heating to 60 ℃, then keeping the temperature and stirring for reaction, detecting the reaction process by using a thin-layer chromatography, cooling to room temperature after the reaction is finished, adding 60mL of saturated sodium carbonate solution, and stirring for reaction for 0.5 h; adding 20mL of ethyl acetate into the reaction system for three times respectively, combining organic layers, washing the organic layers twice with saturated saline solution, combining the organic layers, drying with anhydrous sodium sulfate, evaporating the solvent under reduced pressure to obtain a solid, and recrystallizing with 95% ethanol as a solvent to obtain the compound of the formula Ie, wherein the compound is light yellow solid, and the yield is as follows: 83 percent.
ESI-LRMS m/z:371.6[M+H] + , 1 H NMR(500MHz,DMSO-d6)δ:1.21-1.31(m,2H),1.33(s,3H),1.35-1.43(m,6H),1.47-1.58(m,2H),2.03-2.38(m,4H),2.41-2.48(m,1H),2.50-2.83(m,2H),4.11-4.21(m,1H),4.65(s,2H),6.75(dd,J＝7.1,2.2Hz,1H),6.88(d,J＝2.2Hz,1H),7.21(d,J＝7.1Hz,1H),10.37(s,1H)。
Example 6
The reaction formula is as follows:
a reaction flask was charged with 10mmol of the compound of formula IIf, 12mmol of the compound of formula IIIf and 10mL of ionic liquid [ BMim ]]Br, dissolved by stirring, and then 0.8mmol of catalyst Cu (acac) 2 Continuously stirring for about 0.5h, heating to 80 ℃, stirring again for reaction, detecting the reaction process by using thin-layer chromatography, cooling to room temperature after the reaction is finished, adding 60mL of saturated sodium carbonate solution, and stirring again for reaction for 0.5 h; adding 20mL of ethyl acetate into the reaction system for three times respectively, combining organic layers, washing the organic layers twice with saturated saline solution, combining the organic layers, drying with anhydrous sodium sulfate, evaporating the solvent under reduced pressure to obtain a solid, and recrystallizing with 95% ethanol as a solvent to obtain the compound of the formula If as a white solid with the yield: and 55 percent. ESI-LRMS M/z 317.2[ M + H ]] + , 1 H NMR(500MHz,DMSO-d6)δ:2.03-2.37(m,4H),2.63-2.74(m,2H),2.83-3.19(s,2H),3.40-3.57(m,2H),6.65-6.78(m,1H),6.81-6.94(m,1H),7.03-7.18(m,4H),7.22-7.30(m,3H)，10.7(s,1H)。
Example 7
The reaction formula is as follows:
a reaction flask was charged with 10mmol of the compound of formula IIa, 12mmol of the compound of formula IIIa and 10mL of ionic liquid [ BMMIm ]]BF 4 Stirring to dissolve, adding 0.8mmol of catalyst Co (acac) 2 Continuously stirring for about 0.5h, heating to 80 ℃, stirring for reaction for 7h, detecting the reaction process by thin-layer chromatography, cooling to room temperature after the reaction is finished, adding 60mL of saturated sodium carbonate solution, and stirring for reaction0.5 h; adding 20mL of ethyl acetate into the reaction system for three times respectively, combining organic layers, washing the organic layers twice with saturated saline solution, combining the organic layers, drying with anhydrous sodium sulfate, evaporating the solvent under reduced pressure to obtain a solid, and recrystallizing with 95% ethanol as a solvent to obtain the compound of the formula Ia as a white solid with the yield: 87 percent.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (9)
1. A synthetic method of indole base compounds is characterized in that 3-indoleethylamine compounds shown in a formula II and 3-butynoic acid compounds shown in a formula III react in ionic liquid under the catalysis of acetylacetone metal complex as a catalyst to obtain the indole base compounds shown in the formula I:
wherein:
R 1 is hydrogen, chlorine, methyl, chloromethyl or methoxy;
R 2 is hydrogen or methyl;
R 3 is hydrogen, methyl or ethyl;
R 4 is hydrogen, methyl, cyclohexyl, 4-methylphenyl or benzyl.
2. The method for synthesizing indole base compounds according to claim 1, wherein the compounds of formula II, formula III and formula I in the reaction are selected from the group consisting of:
3. the method for synthesizing indole base compounds according to claim 1, wherein the ionic liquid is [ BMIm]X、[PMIm]X、[HMIm]X、[BMMIm]X、[BMMIm]BF 4 、[EMIm]BF 4 Wherein X is halogen.
4. The method for synthesizing indole base compounds according to claim 1, wherein the metal in the catalyst acetylacetone metal complex is selected from 2-valent metal ions.
5. The method for synthesizing indole base compounds according to claim 4, wherein the metal in the catalyst acetylacetone metal complex is selected from Ni 2+ 、Cu 2+ 、Co 2+ Or Vo 2+ 。
6. The method for synthesizing indoline base compounds according to claim 1, wherein the reaction temperature is 50-80 ℃.
7. The method for synthesizing indole base compounds according to claim 1, wherein the amount of the catalyst is 3% to 8% of the amount of the compound represented by formula II.
8. The method for synthesizing indole base compounds according to any one of claims 1 to 7, wherein the reaction is followed by a post-treatment comprising the steps of:
(1) adding saturated sodium carbonate solution into the reaction solution after the reaction is finished, and continuously stirring for reaction;
(2) adding ethyl acetate into the system for 2-5 times, and combining organic layers;
(3) the organic layer obtained in step (2) was washed with brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure.
9. The method for synthesizing indole base compounds according to claim 8, wherein the step (3) is followed by recrystallization using 95% ethanol as a solvent.
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