CN1834089A - Prepn. of 3-position substituted indole derivative - Google Patents

Prepn. of 3-position substituted indole derivative Download PDF

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CN1834089A
CN1834089A CN 200610050393 CN200610050393A CN1834089A CN 1834089 A CN1834089 A CN 1834089A CN 200610050393 CN200610050393 CN 200610050393 CN 200610050393 A CN200610050393 A CN 200610050393A CN 1834089 A CN1834089 A CN 1834089A
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indoles
substituted indole
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林旭锋
崔孙良
王彦广
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Zhejiang University ZJU
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Abstract

This invention discloses a method to prepare 3-substituted indole derivatives, that is, ionic liquid is adopted as reaction solvent and Michael addition reaction over indole and alpha, beta-unsaturated ketone is catalyzed by palladium chloride at a temperature of 100~130 deg. C for 0.4~3 hours. The mixture is extracted, recrystallized and separated to obtain 3-substituted indole derivatives. The molar ratio of indole to alpha, beta-unsaturated ketone is 1~1.1:1 and the amount of palladium chloride is 0.1~1.5% mole of indole. Compared to existing synthesis method, this invention has the advantages that: a) reaction conditions are soft, no air-isolation is necessary and the reaction time is short; b) palladium as catalyst requires only a small amount; c) ionic liquid as reaction solvent can be recycled and is thus promising; d) raw material preparation and postprocessing are both simple, which is applicable in large-scale industrial production.

Description

A kind of preparation method of 3 3-position substituted indole derivatives
Technical field
The present invention relates to indoles heterocycle synthetic method, relate in particular to a kind of preparation method of 3 3-position substituted indole derivatives.
Background technology
Benzazole compounds not only extensively exists at nature, and have many physiologically actives, being that raw material is synthetic with the indole nucleus has the natural product of physiologically active or a large amount of compound of deriving all is the research core of indoles chemistry for the usefulness of screening active ingredients all the time; Therefore to they research very extensively and profoundly, particularly how more efficiently and greenly the synthesis of indole derivative especially receive people's huge concern.In the middle of various indole derivativeses, the indoles of 3 replacements is the important skeleton of a class in the design of the complete synthesis and molecular drug target of natural product.Therefore, the indole derivatives of 3 replacements of research just is extremely important, and many methods have been reported the preparation method of this compounds.Wherein, a kind of method that simply and directly prepares 3 3-position substituted indole derivatives is protonic acid or Louis acid catalysis indoles and α, the Michael reaction of beta-unsaturated carbonyl compound.For example, (1) document J.Org.Chem.2002, reported in 67,3700 studied indium tribromide can be under the reaction conditions of gentleness effectively catalyzing indole and α, the Michael reaction of beta-unsaturated carbonyl compound; (2) document Tetrahedron Letters 46 (2005) 3859 has reported samarium triiodide effectively catalyzing indole and α, the Michael reaction of beta-unsaturated carbonyl compound; (3) Synlett 2004, No.6, and 944 have reported the another kind of approach of the catalytic michael reaction of trivalent gold salt.Yet the conjugate addition reaction of protonic acid catalyzing indole often needs careful control acid, with the generation of side reactions such as the dimerization that prevents indoles itself or poly.In addition, in the preparation method who has reported, there are many experimentations to relate to the variety of problems such as reagent, low-yield, aftertreatment complexity and long reaction time of strong acid condition, costliness.Thereby in the indoles chemistry, under condition gentleness, eco-friendly, the regioselectivity conjugate addition reaction that solves 3 efficiently is very important.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of 3 3-position substituted indole derivatives.
It is to be reaction solvent with the ionic liquid, under Palladous chloride catalysis, indoles and α, Michael reaction 0.4-3 hour takes place in alpha, beta-unsaturated ketone under 100-130 ℃ of temperature, extraction, recrystallization, separation obtain 3 3-position substituted indole derivatives, the molar equivalent ratio of indoles and alpha, beta-unsaturated ketone is 1-1.1: 1; The consumption of catalyzer Palladous chloride is the 0.1%-1.5% molar equivalent of indoles, and reaction formula is:
Figure A20061005039300041
Wherein X=H, halogen, alkyl, alkoxyl group, wherein alkyl is C nH 2n+1, n=1-4.R 1, R 2=alkyl, aryl, wherein alkyl is C nH 2n+1, n=1-4.
Said ionic liquid reaction solvent 1-methyl-3-butyl imidazole a tetrafluoro borate, 1-methyl-3-butyl imidazole hexafluorophosphate, molecular formula is:
[bmim][BF 4] [bmim][PF 6]
Temperature of reaction is 110-130 ℃; Reaction times is 0.4-2 hour.The molar equivalent ratio of indoles and alpha, beta-unsaturated ketone is 1: 1; The consumption of catalyzer Palladous chloride is the 0.1%-0.5% molar equivalent of indoles.
The present invention compares with existing synthetic method, has the following advantages:
1) the reaction conditions gentleness is reacted without secluding air, and the reaction times is short;
2) use palladium to make catalyzer, consumption seldom;
3) used ionic liquid to be reaction solvent, ionic liquid can be reused, and good prospects for application is arranged;
4) feed intake and aftertreatment all very simple, be easy to realize industrialized production.
Specific implementation method
The general molecular formula of 3 3-position substituted indole derivatives is:
Figure A20061005039300043
Wherein X=H, halogen, alkyl, alkoxyl group, wherein alkyl is C nH 2n+1, n=1-4.R 1, R 2=alkyl, aryl, wherein alkyl is C nH 2n+1, n=1-4.
The preparation method's of 3 3-position substituted indole derivatives concrete reactions steps is as follows:
With the ionic liquid is reaction solvent, under Palladous chloride catalysis, and indoles and α, Michael reaction can take place in alpha, beta-unsaturated ketone under 100-130 ℃, reaction times is 0.4-3 hour, after reaction finishes, obtains 3 3-position substituted indole derivatives through simply extracting to separate with recrystallization process.The recommendation response temperature is 120 ℃; The recommendation response time is 0.5 hour.
Wherein reaction solvent comprises 1-methyl-3-butyl imidazole a tetrafluoro borate, 1-methyl-3-butyl imidazole hexafluorophosphate; The molar equivalent ratio of indoles and alpha, beta-unsaturated ketone is 1-1.1: 1; The consumption of catalyzer Palladous chloride is the 0.1%-1.5% molar equivalent of indoles.
Following examples will help to understand the present invention, but be not limited to content of the present invention:
Embodiment 1
0.01 mole indoles and 0.01 mole 1,3-diphenylprop ketenes is dissolved in 4 milliliters of ionic liquid [bmim] [BF 4] in, add 1.8 milligrams Palladous chloride then, 120 ℃ of stirring reactions 0.5 hour, reaction finishes, and adds the extracted with diethyl ether product, and extraction liquid adds sherwood oil and carries out recrystallization, separate and obtain 3-(1-hydrogen-indol-3-yl)-1,3-phenylbenzene-1-acetone, productive rate 95%.
Figure A20061005039300051
mp?136-138℃；
IR(KBr)：3407(N-H)，1675(C＝O)cm -1.
1H?NMR(500MHz，CDCl 3)：δ＝8.04(br，1H)，7.98(d，J＝7.5Hz，2H)，7.58(t，J＝7.4Hz，1H)，7.45-7.50(m，3H)，7.40(d，J＝7.4Hz，2H)，7.28-7.34(m，3H)，7.17-7.23(m，2H)，7.07(t，J＝7.4Hz，1H)，6.99(s，1H)，5.13(t，J＝7.2Hz，1H)，3.85(dd，J＝6.8，6.8Hz，1H)，3.78(dd，J＝7.6，7.6Hz，1H)ppm. 13C?NMR(125MHz，CDCl 3)：δ＝198.9，144.5，137.3，136.8，133.2，128.8，128.6，128.3，128.0，126.8，126.5，122.3，121.7，119.7，119.6，119.4，111.4，45.4，38.4ppm.
MS(EI)：m/z＝325[M +].
HRMS(EI)：m/z[M] +?calcd?for?C 23H 19NO：325.1467；found：325.1465.
Embodiment 2
0.01 mole indoles and 0.01 mole of 1-phenyl-3-(4 '-bromophenyl) acrylketone are dissolved in 4 milliliters of ionic liquid [bmim] [PF 6] in, add 2.8 milligrams Palladous chloride then, 110 ℃ of stirring reactions 0.4 hour, reaction finishes, and adds the extracted with diethyl ether product, and extraction liquid adds sherwood oil and carries out recrystallization, separate and obtain 3-(1-hydrogen-indol-3-yl)-1-phenyl-3-(4 '-bromophenyl)-1-acetone, productive rate 90%.
Figure A20061005039300052
mp?137-139℃；
IR(KBr)：3340(N-H)，1681(C＝O)cm -1.
1H?NMR(500MHz，CDCl 3)：δ＝8.07(br，1H)，7.97(d，J＝7.5Hz，2H)，7.58(t，J＝7.4Hz，1H)，7.45-7.05(m，3H)，6.99(s，1H)，5.07(t，J＝7.0Hz，1H)，3.85(dd，J＝6.3，6.3Hz，1H)，3.74(dd，J＝8.0，8.0Hz，1H)ppm.
13C?NMR(125MHz，CDCl 3)：δ＝198.4，143.5，137.2，136.8，133.4，129.8，128.9，128.3，126.6，126.0，122.5，122.3，119.8，119.6，119.0，111.5，111.3，45.1，37.9ppm.HRMS(EI)：m/z[M] +calcd?for?C 23H 18BrNO：403.0572；found：403.0575.
Embodiment 3
0.01 mole indoles and 0.01 mole of 1-phenyl-3-(4 '-aminomethyl phenyl) acrylketone are dissolved in 4 milliliters of ionic liquid [bmim] [BF 4] in, add 2.0 milligrams Palladous chloride then, 100 ℃ of stirring reactions 0.5 hour, reaction finishes, and adds the extracted with diethyl ether product, and extraction liquid adds sherwood oil and carries out recrystallization, separate and obtain 3-(1-hydrogen-indol-3-yl)-1-phenyl-3-(4 '-aminomethyl phenyl)-1-acetone, productive rate 92%.
solid；mp?140℃.
IR(KBr)：1672(CO)，3428(NH)cm -1.
1HNMR(400MHz，CDCl 3)：δ＝2.28(s，3H，CH 3)，3.68-3.84(m，2H，CH 2)，5.04(t，J＝7.2Hz，1H，CH)，6.97-7.53(m，12H)，7.91-7.96(m，3H)ppm.
13CNMR(125MHz，CDCl 3)：δ＝198.9，141.4，137.4，136.8，135.9，133.2，129.4，128.8，128.3，127.9，126.9，122.3，121.6，119.8，119.7，119.6，111.3，45.5，38.1，21.2ppm.HRMS：m/z[M]calcd?for?C 24H 21NO：339.1623；found：339.1634[M +].
Embodiment 4
0.01 mole indoles and 0.01 mole of 3-phenyl-1-(4 '-chloro-phenyl-) acrylketone are dissolved in 4 milliliters of ionic liquid [bmim] [PF 6] in, add 2.8 milligrams Palladous chloride then, 120 ℃ of stirring reactions 0.4 hour, reaction finishes, and adds the extracted with diethyl ether product, and extraction liquid adds sherwood oil and carries out recrystallization, separate and obtain 3-phenyl-3-(1-hydrogen-indol-3-yl)-1-(4-chloro-phenyl-)-1-acetone, productive rate 88%.
Figure A20061005039300062
mp?158-160℃.
IR(KBr)：1680(CO)，3445(NH)cm -1.
1H?NMR(400MHz，CDCl 3)：δ＝3.65-3.80(m，2H，CH 2)，5.03(t，J＝7.2Hz，1H，CH)，6.99-7.43(m，12H)，7.84-7.98(m，3H).
HRMS：m/z[M]calcd?for?C 23H 18ClNO：359.0891；found：359.0891[M +].
Embodiment 5
0.01 mole indoles and 0.01 mole of 1-methyl-3-phenyl acrylketone are dissolved in 4 milliliters of ionic liquid [bmim] [BF 4] in, add 1.8 milligrams Palladous chloride then, 120 ℃ of stirring reactions 0.5 hour, reaction finished, and adds the extracted with diethyl ether product, and extraction liquid adds sherwood oil and carries out recrystallization, separates obtaining 3-phenyl-3-(1-hydrogen-indol-3-yl)-2-butanone, productive rate 85%.
Figure A20061005039300071
mp?91-93℃：
IR(KBr)：3406(N-H)，1709(C＝O)cm -1.
1H?NMR(500MHz，CDCl 3)：δ＝8.12(br，1H)，7.51(d，J＝8.0Hz，1H)，7.39-7.11(m，8H)，7.01(s，1H)，4.92(t，J＝7.0Hz，1H)，3.35(dd，J＝7.5，7.5Hz，1H)，3.26(dd，J＝8.0，8.0Hz，1H)，2.15(s，3H)ppm.
HRMS：m/z[M]calcd?for?C 18H 17NO：263.1310；found：263.1310[M +].
Embodiment 6
0.01 mole indoles and 0.01 mole of 3-methyl isophthalic acid-(4 '-isopropyl phenyl) acrylketone are dissolved in 4 milliliters of ionic liquid [bmim] [BF 4] in, add 2.0 milligrams Palladous chloride then, 120 ℃ of stirring reactions 0.5 hour, reaction finishes, and adds the extracted with diethyl ether product, and extraction liquid adds sherwood oil and carries out recrystallization, separate and obtain 3-methyl-3-(1-hydrogen-indol-3-yl)-1-(4-isopropyl phenyl)-1-acetone, productive rate 85%.
Brown?viscous?oil.
1H?NMR(CDCl 3，，400MHz)：δ＝1.25(3H，d，J＝7.0Hz)，1.50(3H，d，J＝7.0Hz)，1.55(3H?d，J＝7.0Hz)，2.42(3H，s)，2.87-3.01(1H，m)，3.39(2H，dd，J＝7.4，16.2Hz)，3.72-3.82(1H，m)，7.07-7.14(3H，m)，7.23-7.27(2H，m)，7.68-7.72(2H，m)，7.82-7.86(2H，m)；
13CNMR(CDCl 3，100MHz)：δ＝12.1，21.0，23.7，27.4，34.2，45.6，110.4，115.6，118.9，119.0，120.6，126.4，127.1，128.2，130.2，135.2，135.4，154.1，199.5；
GC-MS：m/z?158(100)，319(13)；
IR(neat)：738，1680，3039，3357cm -1；
anal.calcd.for?C 22H 25NO：C?82.72，H?7.89，N?4.38；found：C?82.74，H?7.83，N?4.38.
Embodiment 7
0.01 mole 5-bromo indole and 0.01 mole 1,3-diphenylprop ketenes is dissolved in 4 milliliters of ionic liquid [bmim] [BF 4] in, add 2.4 milligrams Palladous chloride then, 130 ℃ of stirring reactions 0.5 hour, reaction finishes, and adds the extracted with diethyl ether product, and extraction liquid adds sherwood oil and carries out recrystallization, separate and obtain 3-(1-hydrogen-5-bromo indole-3-yl)-1,3-phenylbenzene-1-acetone, productive rate 80%.
Figure A20061005039300081
mp?148-150℃
IR(KBr)：3424(N-H)，1666(C＝O)cm -1.
1H?NMR(500MHz，CDCl 3)：δ＝8.07(br，1H)，7.94(d，J＝7.5Hz，2H)，7.55-7.14(m，11H)，6.98(s，1H)，5.02(t，J＝7.0Hz，1H)，3.80(dd，J＝6.3，6.3Hz，1H)，3.70(dd，J＝8.0，8.0Hz，1H)ppm.
13C?NMR(125MHz，CDCl 3)：δ＝198.7，144.0，137.2，135.4，133.4，128.9，128.8，128.6，128.3，127.9，126.7，125.3，122.9，122.2，119.1，112.9，112.8，45.4，38.2ppm.
HRMS：m/z[M]calcd?for?C 23H 18BrNO：403.0572；found：403.0575[M +].
Embodiment 7
0.01 mole 5-methoxyl group indoles and 0.01 mole 1,3-diphenylprop ketenes is dissolved in 4 milliliters of ionic liquid [bmim] [BF 4] in, add 2.0 milligrams Palladous chloride then, 120 ℃ of stirring reactions 0.5 hour, reaction finishes, and adds the extracted with diethyl ether product, and extraction liquid adds sherwood oil and carries out recrystallization, separate and obtain 3-(1-hydrogen-5-methoxyl group indol-3-yl)-1,3-phenylbenzene-1-acetone, productive rate 85%.
Figure A20061005039300091
mp?149-150℃
IR(KBr)：3369(N-H)，1678(C＝O)cm -1.
1H?NMR(500MHz，CDCl 3)：δ＝7.95(d，J＝7.2Hz，2H)，7.90(br，1H)，7.55-7.18(m，8H)，6.96(s，1H)，6.96(s，1H)，6.81(d，J＝6.3Hz，2H)，5.05(t，J＝7.2Hz，1H)，3.84(dd，J＝6.8，6.8Hz，1H)，3.76(s，3H)，3.72(dd，J＝7.6，7.6Hz，1H)ppm.
13C?NMR(125MHz，CDCl 3)：δ＝198.4，153.9，144.2，137.2，133.1，131.8，128.6，128.5，128.2，127.8，127.1，126.3，122.2，119.1，112.3，111.8，101.6，55.9，45.2，38.3ppm.HRMS：m/z[M]calcd?for?C 24H 21NO 2：355.1572；found：355.1570[M +].

Claims (4)

1. the preparation method of a 3-position substituted indole derivative, it is characterized in that with the ionic liquid being reaction solvent, under Palladous chloride catalysis, indoles and α, Michael reaction 0.4-3 hour takes place in alpha, beta-unsaturated ketone under 100-130 ℃ of temperature, extraction, recrystallization, separation obtain 3 3-position substituted indole derivatives, and the molar equivalent ratio of indoles and alpha, beta-unsaturated ketone is 1-1.1: 1; The consumption of catalyzer Palladous chloride is the 0.1%-1.5% molar equivalent of indoles, and reaction formula is:
Wherein X=H, halogen, alkyl, alkoxyl group, wherein alkyl is C nH 2n+1, n=1-4.R 1, R 2=alkyl, aryl, wherein alkyl is C nH 2n+1, n=1-4.
2. the preparation method of a kind of 3 3-position substituted indole derivatives according to claim 1 is characterized in that said ionic liquid reaction solvent 1 monomethyl-3-butyl imidazole a tetrafluoro borate, 1-methyl-3-butyl imidazole hexafluorophosphate.
3. the preparation method of a kind of 3 3-position substituted indole derivatives according to claim 1 is characterized in that said temperature of reaction is 110-130 ℃; Reaction times is 0.4-2 hour.
4. the preparation method of a kind of 3 3-position substituted indole derivatives according to claim 1, the molar equivalent ratio that it is characterized in that said indoles and alpha, beta-unsaturated ketone is 1: 1; The consumption of catalyzer Palladous chloride is the 0.1%-0.5% molar equivalent of indoles.
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CN103012242A (en) * 2012-12-31 2013-04-03 北京大学深圳研究生院 Preparation method of 3-substituted indole derivatives
CN103073454A (en) * 2011-10-25 2013-05-01 中国科学院兰州化学物理研究所 Synthetic method for beta-aminocarbonyl compound, beta-mercapto ketone and beta-alkoxy ketone
CN103172553A (en) * 2013-04-18 2013-06-26 安徽工业大学 Method for catalytic synthesis of beta-indolone by using ionic liquid
CN103880575A (en) * 2014-03-21 2014-06-25 台州学院 Method for preparing beta-amino amide derivatives
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CN103073454A (en) * 2011-10-25 2013-05-01 中国科学院兰州化学物理研究所 Synthetic method for beta-aminocarbonyl compound, beta-mercapto ketone and beta-alkoxy ketone
CN103012242A (en) * 2012-12-31 2013-04-03 北京大学深圳研究生院 Preparation method of 3-substituted indole derivatives
CN103012242B (en) * 2012-12-31 2014-12-17 北京大学深圳研究生院 Preparation method of 3-substituted indole derivatives
CN103172553A (en) * 2013-04-18 2013-06-26 安徽工业大学 Method for catalytic synthesis of beta-indolone by using ionic liquid
CN103172553B (en) * 2013-04-18 2015-05-20 安徽工业大学 Method for catalytic synthesis of beta-indolone by using ionic liquid
CN103880575A (en) * 2014-03-21 2014-06-25 台州学院 Method for preparing beta-amino amide derivatives
CN103880575B (en) * 2014-03-21 2015-06-03 台州学院 Method for preparing beta-amino amide derivatives
CN111471044A (en) * 2020-05-26 2020-07-31 西北大学 Synthesis method of palladium-catalyzed 3-aryl 7-azaindole compound
CN111471044B (en) * 2020-05-26 2021-08-10 西北大学 Synthesis method of palladium-catalyzed 3-aryl 7-azaindole compound

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