[go: up one dir, main page]

CN106892921B - A method of synthesis spiral shell indenes pyrrolopyridines - Google Patents

A method of synthesis spiral shell indenes pyrrolopyridines Download PDF

Info

Publication number
CN106892921B
CN106892921B CN201710116335.3A CN201710116335A CN106892921B CN 106892921 B CN106892921 B CN 106892921B CN 201710116335 A CN201710116335 A CN 201710116335A CN 106892921 B CN106892921 B CN 106892921B
Authority
CN
China
Prior art keywords
synthesizing
methyl
spiroindenepyrrolopyridine
reaction
compounds according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710116335.3A
Other languages
Chinese (zh)
Other versions
CN106892921A (en
Inventor
颜朝国
肖满
韩莹
孙晶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yangzhou University
Original Assignee
Yangzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yangzhou University filed Critical Yangzhou University
Priority to CN201710116335.3A priority Critical patent/CN106892921B/en
Publication of CN106892921A publication Critical patent/CN106892921A/en
Application granted granted Critical
Publication of CN106892921B publication Critical patent/CN106892921B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
    • C07D471/20—Spiro-condensed systems

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Indole Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

A method of synthesis spiral shell indenes pyrrolopyridines belong to technical field of organic synthesis.The present invention, for reactant, by intramolecular nucleophilic addition, after generating cyclic intermediate, then is dehydrated with β-ketones with Enamino-esters, 1,3- indandione and isatin and generates spiral shell [indeno [2,1-e] pyrrolo- [3,4-b] pyridine -10,3'- indoline] class compound.The present invention is not required to anhydrous and oxygen-free reaction condition, by intramolecular nucleophilic addition, after generating cyclic intermediate, then is dehydrated generation, and this method is efficient, easy to operate, high income and environmental-friendly.

Description

A method of synthesis spiral shell indenes pyrrolopyridines
Technical field
The invention belongs to technical field of organic synthesis.
Background technique
Nitrogen-containing heterocycle compound and its derivative have extensive bioactivity, each in medicine, pesticide and life science etc. All occupy extremely important status in a field, the synthesis of these compounds is always the research hotspot of organic synthesis field.Its In, polycyclic azoles have a pharmaceutical activity such as antitumor, antibacterial, anti-inflammatory analgesic, such as pemetrexed, Moxifloxacin, Contain polycyclic pyrrole structure unit in the drugs such as zopiclone.Indone in the bioactive molecules such as natural products, drug, pesticide Class compound is also widely present, and the physiological activity outstanding such as show antitumor, anti-hypertension, antiallergy.Simultaneously ring spreads out indone Biology equally shows a variety of biologies and pharmacological activity, and the alkaloid such as separated from manaca has indone pyridine bone Frame, derivative is found to have phosphodiesterase activity and inhibits Adenosine A2a receptor binding capacity, for treating neurological Property disease and the relevant disease of inflammation (Aran go, G. J.;Cortes, D.; et al., Azafluorenones from Oxandra cf. major and biogenetic considerations [J]. Phytochemistry, 1987,26, 2093-2098).It can be seen that the synthesis of polycyclic pyrrole derivatives and indone and cyclics is by increasingly wider General concern (Rentzea, C.; Meyer, N.; Kast, J.;et al. [P]. Ger. Offen.DE 4301426, 1994.)。
There are many synthetic method about indenopyridine derivative of existing literature report, such as 2007, Manpadi etc. with 1,3- indandione rodenticide, aniline or heterocyclic compound with amino and various aromatic acids are reactant, synthesize various polycyclic indeno pyrroles Acridine compound (Manpadi, M.; Uglinskii, P. Y.; et al. Three-component synthesis and anticancer evaluation of polycyclic indenopyridines lead to the discoveiy of a novel indenoheterocycle with potent apoptosis inducing properties [J]. Org. Biomol Chem., 2007, 5, 3865-3872)；2007, Tu Shujiang et al. by aromatic aldehyde, 1,3- indandione rodenticide and arone, Indenopyridine analog derivative is prepared under the conditions of ammonium acetate is existing；The same year, they were again with the third dicyan of arlydene, thioacetic acid or 4- Methylbenzene phenyl-sulfhydrate and the reaction of 1,3- indandione rodenticide generate indone simultaneously [1,2-b] pyridine compounds (Tu, S. J.; Jiang, B.; et al. An efficient and expeditious microwave assisted synthesis of 4- azafluorenones via a multi-component reaction[J]. Tetrahedron Lett, 2007, 48, 1369-1374)；2012, Verma etc. was reported 6- amino -1,3- dimethyl uracil, aromatic acid, three groups of 1,3- indandione rodenticide Divide with water as solvent, p-methyl benzenesulfonic acid is made to synthesize indenopyridine [2,3- under conditions of catalystd] pyrimidines (Verma,J. K.; Raghuvanshi, K.; et al. An efficient one-pot three-component synthesis of functionalized pyrimido[4,5-b]quinolines and indeno fused pyrido [2,3-d]pyrimidines in water. [J]. Tetrahedron Lett., 2012, 53, 399-402).But this There are some problems in a little methods, including raw materials used expensive or needs are previously prepared to varying degrees, and severe reaction conditions make With toxic solvents, transition-metal catalyst is needed, the reaction time is longer, and yield is lower, and substrate expansion range is small etc., and cannot For synthesizing indeno-pyrrole and pyridine compounds and their.Therefore, develop efficient, economy, greenization and substrate and expand the big indenes of range And the synthetic method of pyrrolopyridines is significant.
Summary of the invention
Technical problem to be solved by the present invention lies in the above problem is overcome, a kind of substrate is provided and expands that range is big, raw material It is easy to get, is easy to operate, without the simple spiral shell [indeno [2,1- of transition-metal catalyste] pyrrolo- [3,4-b] pyridine -10,3'- The synthetic method of dihydroindolines compound.
The technical scheme is that: under the conditions of existing for the solvent and catalyst, first by isatin and 1,3- indandione exists Carry out condensation generation under alkaline condition, then by condensation product and 3- arylamino -1- methyl-1HPyrrole-2,5-diones carry out advanced in years Then amino in the product of addition reaction and carbonyl are carried out nucleophilic addition again by Ke Er addition reaction, then by nucleophilic addition The product of reaction by intramolecular dehydration, finally with the mixed solvent of ethyl acetate and petroleum ether carry out silica gel column chromatography to get Spiral shell [indeno [2,1-e] pyrrolo- [3,4-b] pyridine -10,3'- indoline] class compound；
Reaction formula are as follows:
Wherein, R1For C1~C3Alkyl, phenyl or benzyl or C1~C4It is any in alkyl-substituted phenyl, halogenophenyl It is a kind of；
R2For C1~C3Alkyl, any one in halogen；
R3For C1~C3Alkyl, benzyl, alkoxy carbonyl group, any one in acyl group.
The reaction mechanism is as follows by the present invention:
The present invention, for reactant, by intramolecular nucleophilic addition, generates ring with β-ketones with Enamino-esters, 1,3- indandione and isatin After shape intermediate, then it is dehydrated and generates spiral shell [indeno [2,1-e] pyrrolo- [3,4-b] pyridine -10,3'- indoline] class compound.
The present invention exists using the β-ketones with Enamino-esters, indandione, substitution isatin being easy to get as raw material in no transition-metal catalyst Under, it is not required to anhydrous and oxygen-free reaction condition, by intramolecular nucleophilic addition, after generating cyclic intermediate, then is dehydrated and generates spiral shell [indeno [2,1-e] pyrrolo- [3,4-b] pyridine -10,3'- indoline] class compound.The synthetic method is efficient, easy to operate, yield It is high and environmental-friendly.
Further, R of the present invention1Preferably phenyl, 4- aminomethyl phenyl, 4- methoxyphenyl, 4- halogenophenyl, 4- Halogenophenyl, 3- aminomethyl phenyl, 2- aminomethyl phenyl, 3- methoxyphenyl, 2- methoxyphenyl, 3- halogenophenyl, 2- halogeno-benzene Any one in base, synthetic yield is up to 60%~74%.
The R2Preferably methyl, fluorine, chlorine, any one in bromine, synthetic yield is up to 60%~70%.
The R3It is preferred that the tert-butyl that is positive, benzyl, to methoxy-benzyl, benzyloxycarbonyl group, tertbutyloxycarbonyl, phthalyl Any one in base, p-toluenesulfonyl.Its synthetic yield is up to 60%~74%.
The solvent is preferably ethyl alcohol.Work as R1For to methyl amine benzyl, R2For methyl, R3When for benzyl, use ethyl alcohol as molten Agent, yield is up to 72%.
The catalyst is triethylamine.Work as R1For to methyl amine benzyl, R2For chlorine, R3When for benzyl, use triethylamine as molten Agent, yield is up to 74%.
3- arylamino -1- the methyl-1HThe mixing molar ratio of pyrrole-2,5-diones, 1,3- indandione and isatin It is 1: 1~1.5: 1~1.5.Reaction yield is up to 60%~74% under the molar ratio.
The catalyst and 3- arylamino -1- methyl-1HThe mixing molar ratio of pyrrole-2,5-diones is 0.5~2: 1. Reaction yield is up to 60%~74% under the molar ratio.
The temperature condition of the reaction is 50~100 DEG C.In view of preferred solvent be ethyl alcohol, then select the temperature range as Range of reaction temperature.
It is highly preferred that reaction temperature uses 80 DEG C, the reaction time can be foreshortened to 6 hours.At this temperature, reaction efficiency is most It is high.Temperature is excessively high, overlong time, then by-product increases；Temperature is too low, and the time is too short, then reaction is incomplete.Under the reaction condition Its synthetic yield is up to 60%~74%.
Specific embodiment
Below with reference to embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these realities Apply example.
Embodiment 1: preparation structure formula following 1', 4- dibenzyl -2,5'- dimethyl -1HSpiral shell [indenes [2,1-e] pyrroles [3,4-b] pyridine -10,3'- indoline] -1,2', 3,9 (2H,4H)-tetrone:
0.1085g (0.5mmol) 3-(benzylamino is added in the flask of 5mL original bottom) -1- methyl-1HPyrroles -2,5- two Ketone, 0.0730g (0.5mmol) indandione, 0.1085g (0.5mmol) 5- methyl-N-benzyl isatin, add 15mL ethyl alcohol, Again plus 0.0506g (0.5mmol) triethylamine, it reacts 6 hours, after reaction evaporates solvent dense under conditions of being heated to reflux Contracting, carrying out the processing of column Chromatographic purification using silicagel column can be obtained pure 1', 4- dibenzyl -2,5'- dimethyl -1HSpiral shell [indenes [2, 1-e] pyrroles [3,4-b] pyridine -10,3'- indoline] -1,2', 3,9 (2H,4H)-tetrone, separation yield 72%, structure Characterize data is as follows:
1H NMR (400 MHz, DMSO-d 6 ) δ: 7.56 (d, J = 7.2 Hz, 2H, ArH), 7.48-7.41 (m, 5H, ArH), 7.38-7.32 (m, 5H, ArH), 7.31-7.27 (m, 2H, ArH), 7.09 (s, 1H, ArH), 7.00 (d, J = 8.0 Hz, 1H, ArH), 6.63 (d, J = 8.0 Hz, 1H, ArH), 5.91 (brs, 2H, CH2), 4.99 (s, 2H, CH2), 2.79 (s, 3H, CH3), 2.20 (s, 3H, CH3); 13C NMR (100 MHz, DMSO-d 6 ) δ: 189.9, 175.9, 167.1, 164.5, 158.1, 141.0, 140.3, 137.5, 136.5, 135.6, 133.7, 133.4, 132.7, 132.2, 131.1, 129.7, 129.5, 128.8, 127.9, 127.6, 127.4, 126.0, 125.6, 123.5, 122.1, 114.1, 111.3, 109.2, 50.0, 45.9, 44.0, 23.9, 21.0; IR (KBr) υ: 3062, 2936, 1766, 1711, 1650, 1602, 1550, 1495, 1454, 1418, 1382, 1341, 1309, 1283, 1186, 1069, 1032, 1012, 974, 925, 861, 805, 767, 740, 709 cm-1; MS (m/z): HRMS (ESI) C37H27N3NaO4 ([M+Na]+) theoretical value 600.1894 measured value 600.1893.
Embodiment 2: the following 5'- chloro-2-methyl -4- p-methylphenyl -1H- spiral shell [indenes [2,1- of preparation structure formulae] pyrroles [3,4-b] pyridine -10,3'- indoline] -1,2', 3,9 (2H,4H)-tetrone:
In embodiment 1,3-(benzylamino used) -1- methyl-1HThe 3- of pyrrole-2,5-diones equimolar amounts (p-methylphenyl amino) -1- methyl-1HThe replacement of pyrroles -2,5- diketone, 5- methyl-N-benzyl isatin equimolar used The 5- chlorisatide of amount is replaced, other steps are identical as example 1, obtain 5'- chloro-2-methyl -4- p-methylphenyl -1H- spiral shell [indenes [2,1-e] pyrroles [3,4-b] pyridine -10,3'- indoline] -1,2', 3,9 (2H,4H)-tetrone, separation yield 70%, Structural characterization data are as follows:
1H NMR (600 MHz, DMSO-d 6 ) δ: 10.84 (s, 1H, NH), 7.79 (brs, 1H, ArH), 7.60 (brs, 1H, ArH), 7.56 (brs, 1H, ArH), 7.43 (d, J = 6.6 Hz, 2H, ArH), 7.29-7.26 (m, 3H, ArH), 7.15-7.12 (m, 1H, ArH), 6.89 (d, J = 8.4 Hz, 1H, ArH), 5.52 (d, J = 7.2 Hz, 1H, ArH), 2.71 (s, 3H, CH3), 2.49 (s, 3H, CH3); 13C NMR (100 MHz, DMSO-d 6 ) δ: 189.9, 177.2, 167.3, 163.1, 157.0, 141.1, 140.5, 140.4, 136.2, 134.7, 132.9, 132.8, 131.0, 130.3, 129.4, 126.4, 125.8, 122.1, 121.9, 112.9, 111.1, 109.6, 46.5, 23.6, 21.4; IR (KBr) υ: 3394, 3035, 1713, 1657, 1619, 1555, 1511, 1476, 1442, 1376, 1339, 1310, 1249, 1207, 1178, 1121, 1076, 1032, 1008, 974, 903, 824, 766, 739, 721 cm-1; MS (m/z): HRMS (ESI) C29H18ClN3NaO4 ([M+Na]+) theoretical value be 530.0878, measured value 530.0868.
Embodiment 3: the following 1'- benzyl -5'- chloro-2-methyl -4- p-methylphenyl -1 of preparation structure formulaHSpiral shell [indeno [2, 1-e] pyrrolo- [3,4-b] pyridine -10,3'- indoline] -1,2', 3,9 (2H, 4H) tetrone:
3-(benzylamino used) -1- methyl-1HThe 3-(p-methylphenyl ammonia of pyrrole-2,5-diones equimolar amounts Base) -1- methyl-1HThe replacement of pyrroles -2,5- diketone, the chloro- N- benzyl of 5- of 5- methyl-N-benzyl isatin equimolar amounts used The replacement of base isatin, other steps are identical as example 1, obtain 1'- benzyl -5'- chloro-2-methyl -4- p-methylphenyl -1HSpiral shell [indeno [2,1-e] pyrrolo- [3,4-b] pyridine -10,3'- indoline] -1,2', 3,9 (2H, 4H) tetrone, separation yield 70%, Structural characterization data are as follows:
1H NMR (400 MHz, DMSO-d 6 ) δ: 7.83-7.81 (m, 1H, ArH), 7.73 (d, J = 2.4Hz, 1H, ArH), 7.62-7.61 (m, 1H, ArH), 7.57 (brs, 1H, ArH), 7.55 (brs, 1H, ArH), 7.44 (d, J = 8.0 Hz, 2H, ArH), 7.38 (t, J = 8.0 Hz, 2H, ArH), 7.32-7.27 (m, 4H, ArH), 7.18-7.14 (m, 1H, ArH), 6.79 (d, J = 8.4 Hz, 1H, ArH), 5.55 (d,J = 7.6 Hz, 1H, ArH), 5.04 (s, 2H, CH2), 2.74 (s, 3H, CH3), 2.50 (s, 3H, CH3) ; 13C NMR (100 MHz, DMSO-d 6 ) δ: 190.0, 175.8, 167.3, 163.0, 157.2, 141.5, 140.7, 140.5, 136.2, 136.0, 135.3, 134.6, 133.0, 132.7, 131.1, 130.3, 129.4, 128.9, 127.7, 127.4, 127.3, 125.8, 124.7, 122.3, 122.0, 112.5, 110.8, 109.3, 46.0, 44.0, 23.7, 21.4; IR (KBr) υ: 3059, 2937, 1881, 1774, 1715, 1690, 1653, 1608, 1549, 1513, 1483, 1454, 1429, 1374, 1338, 1258, 1195, 1173, 1105, 1076, 1031, 999, 942, 898, 869, 824, 766, 743 cm-1; MS (m/z): HRMS (ESI) C36H24ClN3NaO4 ([M+Na]+) theoretical value 620.1348, measured value 620.1340.
Embodiment 4: the following chloro- 4-(4- chlorphenyl of 1'- benzyl -5'- of preparation structure formula) -2- methyl-1 H- spiral shell [indeno [2,1-e] pyrrolo- [3,4-b] pyridine -10,3'- indoline] -1,2', 3,9 (2H, 4H) tetrone:
3-(benzylamino used) -1- methyl-1HThe 3-(rubigan ammonia of pyrrole-2,5-diones equimolar amounts Base) -1- methyl-1HThe replacement of pyrroles -2,5- diketone, the chloro- N- benzyl of 5- of 5- methyl-N-benzyl isatin equimolar amounts used The replacement of base isatin, other steps are identical as example 1, obtain the chloro- 4-(4- chlorphenyl of 1'- benzyl -5'-) -2- methyl-1 H- spiral shell [indenes And [2,1-e] pyrrolo- [3,4-b] pyridine -10,3'- indoline] -1,2', 3,9 (2H, 4H) tetrone, separation yield is 62%, structural characterization data are as follows:
1H NMR (400 MHz, DMSO-d 6 ) δ: 7.85 (brs, 1H, ArH), 7.75-7.70 (m, 3H, ArH), 7.56 (d, J = 7.6 Hz, 2H, ArH), 7.45-7.35 (m, 3H, ArH), 7.34-7.28 (m, 4H, ArH), 7.25-7.21 (m, 1H, ArH), 6.79 (d, J = 8.4 Hz, 1H, ArH), 5.63 (d, J = 7.6 Hz, 1H, ArH), 5.04 (s, 2H, CH2), 2.74 (s, 3H, CH3); 13C NMR (100 MHz, DMSO-d 6 ) δ: 189.9, 175.7, 167.3, 163.1, 156.8, 141.5, 140.5, 136.1, 136.0, 135.5, 135.2, 133.2, 132.6, 131.7, 131.2, 129.9, 129.5, 129.4, 128.9, 127.8, 127.4, 127.3, 125.9, 122.2, 121.5, 112.6, 110.8, 109.6, 46.0, 44.0, 43.8, 23.7; IR (KBr) υ: 3059, 2932, 1766, 1711, 1659, 1609, 1555, 1492, 1453, 1442, 1370, 1340, 1253, 1170, 1091, 1032, 1010, 896, 856, 818, 763, 741, 700 cm-1; MS (m/z): HRMS (ESI) C35H21Cl2N3NaO4 ([M+Na]+) theoretical value 640.0801, measured value 640.0792.
Show that the present invention provides one kind to pass through multi-component reaction, one-step synthesis spiral shell [indeno by the example of above-mentioned offer [2,1-e] pyrrolo- [3,4-b] 10,3 '-indoline of pyridine -] and class compound method, there is this method raw material to be easy to get, nothing Transition-metal catalyst, easy to operate, high income and substrate is needed to expand the big advantage of range.

Claims (8)

1.一种合成螺茚吡咯并吡啶类化合物的方法，其特征在于：在溶剂和催化剂三乙胺存在的条件下，先将取代有R2和R3的靛红与1,3-茚满二酮在碱性条件下进行缩合生成，再将缩合产物与3- R1基团-氨基-1-甲基-1H-吡咯-2,5-二酮进行迈克尔加成反应，然后再将加成反应的产物中氨基与羰基进行亲核加成反应，再将亲核加成反应的产物通过分子内脱水，最后用乙酸乙酯和石油醚的混合溶剂进行硅胶柱层析，即得螺[茚并[2,1-e]吡咯并[3,4-b]吡啶-10,3'-二氢吲哚]类化合物；反应通式为：1. a method for synthesizing spiroindenepyrrolopyridine compounds, is characterized in that: under the condition that solvent and catalyzer triethylamine exist, first isatin and 1,3-indan substituted with R 2 and R 3 The diketone is condensed under basic conditions to form, and then the condensation product is subjected to Michael addition reaction with 3-R 1 group-amino-1-methyl-1 H -pyrrole-2,5-dione, and then the In the product of the addition reaction, the amino group and the carbonyl group are subjected to a nucleophilic addition reaction, and then the product of the nucleophilic addition reaction is subjected to intramolecular dehydration, and finally silica gel column chromatography is performed with a mixed solvent of ethyl acetate and petroleum ether to obtain the spiro [Indeno[2,1- e ]pyrrolo[3,4- b ]pyridine-10,3'-indoline] compounds; the general reaction formula is: 其中，R1为C1～C3的烷基、苯基或苄基，或C1～C4烷基取代苯基、卤代苯基中的任意一种；Wherein, R 1 is C 1 -C 3 alkyl, phenyl or benzyl, or any one of C 1 -C 4 alkyl-substituted phenyl, halogenated phenyl; R2为C1～C3的烷基、卤素中的任意一种；R 2 is any one of C 1 -C 3 alkyl and halogen; R3为C1～C3的烷基、苄基、烷氧羰基、酰基中的任意一种。R 3 is any one of a C 1 -C 3 alkyl group, a benzyl group, an alkoxycarbonyl group, and an acyl group. 2.根据权利要求1所述合成螺茚吡咯并吡啶类化合物的方法，其特征在于：所述R1为苯基、4-甲基苯基、4-甲氧基苯基、4-卤代苯基、3-甲基苯基、2-甲基苯基、3-甲氧基苯基、2-甲氧基苯基、3-卤代苯基、2-卤代苯基中的任意一种。2. the method for synthesizing spiro-indenepyrrolopyridine compounds according to claim 1, is characterized in that: described R 1 is phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-halogenated Any one of phenyl, 3-methylphenyl, 2-methylphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 3-halophenyl, 2-halophenyl kind. 3.根据权利要求1所述合成螺茚吡咯并吡啶类化合物的方法，其特征在于：所述R2为甲基、氟、氯、溴中的任意一种。3. The method for synthesizing spiroindenepyrrolopyridine compounds according to claim 1, wherein the R 2 is any one of methyl, fluorine, chlorine and bromine. 4.根据权利要求1所述合成螺茚吡咯并吡啶类化合物的方法，其特征在于：所述溶剂为乙醇。4. The method for synthesizing spiroindenepyrrolopyridine compounds according to claim 1, wherein the solvent is ethanol. 5.根据权利要求1或2或3或4所述合成螺茚吡咯并吡啶类化合物的方法，其特征在于：所述3-芳基氨基-1-甲基-1H-吡咯-2,5-二酮、1,3-茚满二酮与靛红的混合摩尔比为1∶1～1.5∶1～1.5。5. The method for synthesizing spiroindenepyrrolopyridines according to claim 1 or 2 or 3 or 4, wherein the 3-arylamino-1-methyl- 1H -pyrrole-2,5 The mixed molar ratio of -diketone, 1,3-indandione and isatin is 1:1-1.5:1-1.5. 6.根据权利要求5所述合成螺茚吡咯并吡啶类化合物的方法，其特征在于：所述催化剂和3-芳基氨基-1-甲基-1H-吡咯-2,5-二酮的混合摩尔比为0.5～2∶1。6. The method for synthesizing spiroindenepyrrolopyridine compounds according to claim 5, wherein the catalyst and 3-arylamino-1-methyl- 1H -pyrrole-2,5-dione have The mixing molar ratio is 0.5 to 2:1. 7.根据权利要求1所述合成螺茚吡咯并吡啶类化合物的方法，其特征在于：所述反应的温度条件为50～100℃。7 . The method for synthesizing spiroindenepyrrolopyridine compounds according to claim 1 , wherein the temperature condition of the reaction is 50-100° C. 8 . 8.根据权利要求7所述合成螺茚吡咯并吡啶类化合物的方法，其特征在于：所述反应的温度条件为80℃。8 . The method for synthesizing spiroindenepyrrolopyridine compounds according to claim 7 , wherein the temperature condition of the reaction is 80° C. 9 .
CN201710116335.3A 2017-03-01 2017-03-01 A method of synthesis spiral shell indenes pyrrolopyridines Active CN106892921B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710116335.3A CN106892921B (en) 2017-03-01 2017-03-01 A method of synthesis spiral shell indenes pyrrolopyridines

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710116335.3A CN106892921B (en) 2017-03-01 2017-03-01 A method of synthesis spiral shell indenes pyrrolopyridines

Publications (2)

Publication Number Publication Date
CN106892921A CN106892921A (en) 2017-06-27
CN106892921B true CN106892921B (en) 2019-04-05

Family

ID=59185712

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710116335.3A Active CN106892921B (en) 2017-03-01 2017-03-01 A method of synthesis spiral shell indenes pyrrolopyridines

Country Status (1)

Country Link
CN (1) CN106892921B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107311849B (en) * 2017-07-24 2020-04-07 扬州大学 Synthetic method of ring-bridged spiroindanone compound
CN107936018A (en) * 2017-12-21 2018-04-20 扬州大学 Spiral shell [1 pyrrolo- of acenaphthylene [3,4 b] pyridine] class compound and its synthetic method
CN115414356A (en) * 2022-09-27 2022-12-02 广西科技大学 Application of indenopyrrole derivatives in preparation of antitumor pharmaceutical composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Chao Wang et al..Efficient synthesis of functionalized spiro[indoline-3,4 -pyrrolo[3,4-b]pyridines] via one-pot three-component reaction.《Mol Divers》.2014,第18卷809-820. *

Also Published As

Publication number Publication date
CN106892921A (en) 2017-06-27

Similar Documents

Publication Publication Date Title
Shaabani et al. 5-Amino-pyrazoles: potent reagents in organic and medicinal synthesis
Paul et al. Three-component synthesis of a polysubstituted pyrrole core containing heterocyclic scaffolds over magnetically separable nanocrystalline copper ferrite
Zhang et al. Solid acid-catalyzed domino cyclization reaction: regio-and diastereoselective synthesis of pyrido [2, 3-d] pyrimidine derivatives bearing three contiguous stereocenters
Verniest et al. Synthesis of substituted β-carbolines via gold (III)-catalyzed cycloisomerization of N-propargylamides
JP2005518369A (en) Imidazolidines, pyrimidines and triazines for enhancing recognition as GABA-Aα5 receptor subtype ligands
CN106892921B (en) A method of synthesis spiral shell indenes pyrrolopyridines
FI95259B (en) Process for the preparation of pharmaceutically active 7-substituted-2-amino-3,5-dihydro-4H-pyrrolo / 3,2-d / pyrimidin-4-ones
CN112194634B (en) A kind of preparation method of N-difluoromethylimidazolium sulfur (seleno) urea derivative
Sroor et al. A facile and robust approach for synthesis and structural characterization of an unprecedented ring system of 4H-pyrazolo [3, 4-f] indolizine-4, 9 (2H)-dione derivatives
CN110437236A (en) A kind of indoles -1,2- and 1,4- benzodiazepine compounds and its synthetic method
Awasthi et al. A three-component, general and practical route for diastereoselective synthesis of aza-spirocyclic pyrazolones via a decarboxylative annulation process
Wang et al. Microwave-assisted chemoselective reaction: a divergent synthesis of pyrazolopyridine derivatives with different substituted patterns
Xiao et al. Iron-Catalyzed One-Pot Synthesis of Indole-Tethered Tetrasubstituted Pyrroles and Their Transformations to Indolizino [8, 7-b] indole Derivatives
Spano et al. Convenient synthesis of pyrrolo [3, 4-g] indazole
Sharma et al. Synthesis of novel fluorinated multisubstituted pyrimidines and 1, 5-benzodiazepines via fluorinated N, S-acetals
Pierce et al. Synthesis of novel 3, 4-diaryl-5-aminopyrazoles as potential kinase inhibitors
CN106977524B (en) A kind of synthetic method of phenanthro- furans and azoles
Song et al. Facile microwave-assisted synthesis of benzimidazole scaffolds via Ugi-type three-component condensation (3CC) reactions
Tang et al. Synthesis of 8-bromo-7-chloro [1, 2, 4] triazolo [4, 3-c] pyrimidines, their ring rearrangement to [1, 5-c] analogues, and further diversification
CN104710426B (en) Benzopyrrolizidine alkaloid and its preparation method and use
Zhang et al. Synthesis and anti-proliferative activity evaluation of novel 1, 4-naphthoquinones possessing pyrido [2, 3-d] pyrimidine scaffolds
Fukuda et al. A Synthesis of Lamellarins via Regioselective Assembly of 1, 2, 3-Differentially Substituted 5, 6-Dihydropyrrolo [2, 1-a] Isoquinoline Core
Tandon et al. Synthesis of 3, 6-diaryl-1 H-pyrazolo [3, 4-b] pyridines via one-pot sequential Suzuki–Miyaura coupling
Sreenivas et al. Copper-mediated domino synthesis of pyrimido [4, 5-b] carbazolones via Ullmann N-arylation and aerobic oxidative C–H amidation
Messaoudi et al. Stepwise synthesis of 2, 6-difunctionalized ethyl pyrazolo [1, 5-a] pyrimidine-3-carboxylate via site-selective cross-coupling reactions: experimental and computational studies

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant