Synthesis of Indanone-Containing Heterocycles via Cycloaddition Reaction of Quinolinium Ylides with 1, 3-Indanedione and 2-Arylidene-1, 3-indanediones

Citation: Ding Bangdong, Jiang Yechao, Zhang Yu, Ye Rong, Sun Jin, Yan Chaoguo. Synthesis of Indanone-Containing Heterocycles via Cycloaddition Reaction of Quinolinium Ylides with 1, 3-Indanedione and 2-Arylidene-1, 3-indanediones[J]. Chinese Journal of Organic Chemistry, 2020, 40(4): 1003-1016. doi: 10.6023/cjoc201910016 shu

喹啉季铵盐和1, 3-茚满二酮及2-芳亚甲基1, 3-茚满二酮的环加成反应合成茚满酮类含氮杂环化合物

丁邦东 ^a, ,
姜业朝 ^a, ,
张瑜 ^b, ,
叶蓉 ^b, ,
孙晶 ^b, ,
颜朝国 ^{b,
,}

a.
扬州工业职业技术学院化学工程学院江苏扬州 225127
b.
扬州大学化学化工学院江苏扬州 225002

通讯作者: 颜朝国, cgyan@yzu.edu.cn

基金项目:
国家自然科学基金 21572196

国家自然科学基金(No.21572196)和江苏省优势学科建设工程资助项目

摘要: 在三乙胺存在下，N-苯甲酰基甲基喹啉溴化物和1，3-茚满二酮在乙醇中于室温反应，主要产物为多取代二氢吡咯[1，2-a]喹啉，次要产物为2-(1-苯甲酰基甲基)喹啉-4-亚基)-1，3-茚满二酮.在相同条件下，N-苄基喹啉溴化物和1，3-茚满二酮在乙醇中于室温反应，主要产物则为2-(1-苯甲酰基甲基)喹啉-4-亚基)-1，3-茚满二酮.另一方面，N-苯甲酰基甲基和N-乙氧羰基甲基以及N-(对硝基苄基)喹啉溴化物和芳香醛，1，3-茚满二酮的三组分反应，在三乙胺存在下在乙醇中高效地生成螺[茚满-2，3'-吡咯[1，2-a]喹啉]衍生物，反应具有很好的非对映选择性.

关键词:

English

Synthesis of Indanone-Containing Heterocycles via Cycloaddition Reaction of Quinolinium Ylides with 1, 3-Indanedione and 2-Arylidene-1, 3-indanediones

a.
College of Chemical Engineering, Yangzhou Polytechnic Institute, Yangzhou, Jiangsu 225127
b.
College of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002

Corresponding author: Yan Chaoguo, cgyan@yzu.edu.cn

Received Date: 12 October 2019
Revised Date: 13 November 2019
Available Online: 25 April 2020
Fund Project:

Project supported by the National Natural Science Foundation of China (No. 21572196) and the Priority Academic Program Development of Jiangsu Higher Education Institutions

Abstract: The triethylamine promoted cycloaddition reaction of N-phenacylquinolinium bromide with 1, 3-indanedione gave functionalized dihydropyrrolo[1, 2-a]quinolines as main products and 2-(1-(2-oxo-2-phenylethyl)-quinolin-4-ylidene)-indene-1, 3-diones as minor products. The similar reaction with N-benzylquinolinium bromide gave 2-(1-(2-oxo-2-phenylethyl)-quino-lin-4-ylidene)-indene-1, 3-diones as major products. On the other hand, triethylamine promoted three-component reaction of N-phenacyl, N-ethoxycarbonylmethyl and N-(4-nitrobenzyl)quinolinium salts, aromatic aldehydes and 1, 3-indanedione in ethanol at room temperature afforded functionalized spiro[indene-2, 3'-pyrrolo[1, 2-a]quinolone]s in good yields and with high diastereoselectivity.

Key words:

1. Introduction

Indanone-containing heterocycle is one of the important heterocyclic scaffolds. They not only present in various alkaloids with a broad array of biological functions, ^[1] but also were widely used in the various materials such as nonlinear optical, organic photovoltaics and semiconductors.^[2] Therefore, the synthesis of indanone-containing heterocycles has attracted much attentions in recent years.^{[3, 4]} It has been known that the readily available 1, 3-indanedione and 2-arylidene-1, 3-indanediones were regarded as the starting active substrates because they had three contiguous electrophilic and nucleophilic reactive sites and were widely used in various cycloaddition reactions.^[5~8] The heteroaromatic N-ylides such as pyridinium, thiazolium, quinolinium, isoquinolinium methylides are special kinds of reactive azomethine ylide, which can be easily generated in situ from deprotonation of their precursor pyridinium salts and their benzo-fused analogs in the reaction system.^{[9, 10]} The heteroaromatic ylides have been widely used to react with versatile electron-deficient alkenes in 1, 3-dipolar cycloadditions for the synthesis of the various heterocycles.^[11~14] In these reactions, heteroaromatic ylides displayed diverse reactivity depending the structures of the substrates and reaction conditions.^{[15, 16]} The cycloaddition reaction of the heteroaromatic N-ylides with readily accessible 2-arylidene-1, 3-indanedione derivatives has been reported to give various fused and spirocyclic indanone derivatives. it has been reported that base promoted reaction of N-phenacylpyridium salts with in situ generated 2-arylidene-1, 3-indandione to give spiro[cyclopropane-1, 2'-inden]-1′, 3'-diones in conventional heating state.^[17a] The similar reaction afforded dihydroindeno[1, 2-b]furans under microwave-irradiation in solvent-free conditions.^[17b] The base mediated reaction of N-phenacylbenzothiazolium bromides, aromatic aldehydes and indane-1, 3-dione afforded functionalized spiro[benzo[d]-pyrrolo[2, 1-b]thia-zole-3, 2'-indene]s in good yields and with high diastereoselectivity.^[18a] On the other hand, The base mediated three-component reaction of N-alkoxycarbonylmethyl- isoquinolinium salts, aromatic aldehydes and 1, 3-indane- dione afforded the unprecedented complex polycyclic compounds, in which the generated isoquinolinium ylide not only behaved as reactive 1, 3-dipoles, but also acted as useful diene to accomplish sequential two 1, 3-dipolar cycloadditions and one Diels-Alder reaction.^[18b] Additionally, reactions of N-cyanomethylisoquinolinium chloride with 2-arylidene-1, 3-indanediones afforded unique spiro- [benzo[f]imidazo[5, 1, 2-cd]indolizine-4, 2'-indene] derivatives by domino cyclization process.^[18c] However, the similar cycloaddition reaction of quinolinium salts with 2-arylidene-1.3-indanediones has not reported until now. For further exploring the molecular diversity of the heteroaromatic ylides in the cycloaddition reactions, herein, we wish to report the base promoted cycloaddition reaction of various quinolinium ylides with 1, 3-indanedione or 2-arylidene-1, 3-indanediones for the convenient synthesis of functionalized dihydropyrrolo[1, 2-a]quinolines, 2-(1-(2- oxo-2-phenylethyl)quinolin-4-ylidene)indene-1, 3-diones and spiro[indene-2, 3'-pyrrolo[1, 2-a]quinoline]s.

2. Results and discussion

According to our previously established reaction conditions for the reaction of N-phenacylpyridinium salts and isoquinolinium salts with aromatic aldehydes and 1, 3-in- danedione, ^[18] an equal amount of N-phenacylquino- linium bromide and 1, 3-indanedione was stirred in ethanol in the presence of triethylamine at room temperature for 4 h. After workup, the functionalized dihydropyrrolo[1, 2-a]qui- noline (1a) was obtained in about 30% yield and 2-(1- (2-oxo-2-phenylethyl)quinolin-4-ylidene)-indene-1, 3-dione (2a) was also obtained in 10% yield. When excess amount of N-phenacylquinolinium bromide was employed in the reaction, the yield of product 1a was increased to 64% yield, while the product 2a was obtained in 12% yield. The structural analysis indicated that two N-phenacylquino- linium bromides took part in the reaction. The unusual feature of the product 1a is that one of quinoline ring was opened and another quinolone ring incorporated into dihydropyrrolo[1, 2-a]quinoline. The product 2a was formed from the nucleophilic reaction at the C-4-position of the quinolinium bromides. A literature survey indicated that although there is no reports about the formation of the product 1a, while the similar products to 2a have been reported by the base promoted reactions of pyridinium salts or isoquinolinium salts with some dicarbonyl compounds such as 1, 3-cyclohexandione.^[19] Then, the CH₃, Cl, Br substituted N-phenacylquinolinium bromides and alkoxy- carbonylmethylquinolinium bromides were employed in the reaction under same reaction conditions. The corresponding main products 1a~1f and minor products 2a~2f were successfully obtained (Table 1). It should be pointed out that products 2c and 2e were not obtained due to too lower yields. The structures of the compounds were fully characterized by IR, HRMS, ¹H NMR and ¹³C NMR spectra and were confirmed by determination of the single crystal structures of compounds 1a (Figure 1), 1f (Figure s1) and 2a (Figure 2). Compounds 1a~1f has stronger purple red color in common organic solvent due to its longer π-conjugated structure. On the other hand, it is difficult to get high qualified NMR spectra due to their lower solubility in organic solvent. The same relative configuration was observed in the two single crystal structures of the compounds 1a and 1f, in which the neighboring aryl group and benzoyl group (or ethoxycarbonyl group) exist on trans-position.

Table 1

Table 1. Reaction of quinolinium salts with 1, 3-indanedione^a

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Entry	R	1	Yield^b/% of 1	2	Yield^b/% of 2
1	C₆H₅	1a	59	2a	12
2	p-CH₃C₆H₄	1b	61	2b	13
3	p-ClC₆H₄	1c	65	2c
4	p-BrC₆H₄	1d	58	2d	14
5	OMe	1e	57	2e
6	OEt	1f	63	2f	10
^a Reaction conditions: quinolinium salt (1.2 mmol), 1, 3-indanedione (0.5 mmol), Et₃N (1.5 mmol), EtOH (15.0 mL), r.t., 4 h; ^b Isolated yields.

Figure 1

Figure 1. Single crystal structure of compound 1a

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Figure 2

Figure 2. Single crystal structure of compound 2a

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In order to develop the scope of the reaction, the reaction of various N-benzylquinolinium bromides with 1, 3- indanedione was also investigated under the same reaction conditions. The results were summarized in Table 2. The reaction successfully afforded 2-(1-benzylquinolin-4-yli- dene)-indene-1, 3-diones 3a~3j in good yields. In these cases, the reaction predominately took part on the C-4-position of N-benzylquinolinium salts, which is very different to that of the above mentioned N-phenacylquino- linium salts. The results showed that N-phenacylquinoli- nium bromides and N-benzylquinolinium bromides have different reactivity and regioselectivity. The substituents on the benzyl group showed little effect on the yields of the products. Additionally, the reaction with N-n-butylquinoli- nium bromide also gave product 3k as the main product. On the other hand, when N-benzyl-4-methylquinolinium bromide was used in the reaction, 2-(1-benzyl-4-methyl- quinolin-2-ylidene)indene-1, 3-diones 3l~3o were produced, which was clearly due to the methyl group occupying at C-4-position of quinoline ring, and the reaction took part on the C-2-position. The single crystal structures of compounds 3a (Figure 3), 3g, 3k and 3l (Figure 4) were successfully determined, which confirmed the structures of compounds 3a~3l.

Table 2

Table 2. Reactions of N-benzylquinolinium salts with 1, 3-in- danedione^a

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Entry	Compd.	R	Ar	Yield/%
1	3a	H	C₆H₅	68
2	3b	H	p-CH₃OC₆H₄	72
3	3c	H	p-CH₃C₆H₄	71
4	3d	H	p-t-BuC₆H₄	77
5	3e	H	3, 5-(CH₃O)₂C₆H₃	76
6	3f	H	p-ClC₆H₄	75
7	3g	H	m-ClC₆H₄	78
8	3h	H	p-BrC₆H₄	73
9	3i	H	p-CF₃C₆H₄	75
10	3j	H	p-NO₂C₆H₄	77
11	3k	H	n-Pr	70
12	3l	CH₃	C₆H₅	72
13	3m	CH₃	p-FC₆H₄	72
14	3n	CH₃	p-ClC₆H₄	78
15	3o	CH₃	p-BrC₆H₄	77
^a Reaction conditions: quinolinium salt (0.5 mmol), 1, 3-indanedione (0.5 mmol), Et₃N (1.0 mmol), EtOH (15.0 mL), r.t., 4 h; ^b Isolated yields.

Figure 3

Figure 3. Single crystal structure of compound 3a

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Figure 4

Figure 4. Single crystal structure of the compound 3l

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For explaining the formation of different kinds of products, a plausible reaction mechanism was proposed in Scheme 1. In the basic medium, quinolinium salt was deprotonated to give quinolinium ylide. On the other hand, 1, 3-indanedione could also be deprotonated to give corre-sponding carbanium ion. Therefore, the nucleophilic addition of generated carbanium ion to quinolinium ylide at both C-2 and C-4 position resulted in intermediates A and B. Secondly, the immigration of negative charge in the intermediates A and B resulted in the more stable carbanium species C and D. Then, carbanium species C and D were dehydrogenated in air to afford enedione intermediate E and 2. It might be duo to the more stability of enedione unit at C-4-position, product 2 became isolated stable product, while the enedione unit at C-2-position in the intermediate E showed high electrophilic property. The further 1, 3-dipolar cycloaddition of quinolinium ylide with the intermediate E gave a polycyclic intermediate F, which in turn was transferred to the intermediate G by partial oxidation in air. At last, the ring-opening of the cyclic enamino unit in the intermediate G gave final product 1. The similar reaction N-benzylqunolinium salts with 1, 3-indanedione was obviously obeyed similar reaction mechanism. The reaction mainly gave product 3 with the stable enedione unit at C-4-position.

Scheme 1

Scheme 1. Plausible reaction mechanism

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The thee-component reaction of N-phenacylquinolinium salts, aromatic aldehydes and 1, 3-indanedione was also carried out in ethanol in the presence of triethylamine as base. The reaction proceeded smoothly at room temperature to give the expected polysubstituted spiro[indene- 2, 3'-pyrrolo[1, 2-a]quinoline]s 4a~4l in good yields (Table 3). The results showed that N-phenacylquinolinium salts showed very different reaction to that of the corresponding N-phenacylpyridinium slats and N-phencylisoquinolinium salts.^[18] The spiro compounds 4a~4l were not very stable in solution and must be quickly isolated by washing the crude product in cold ethanol. In convenience, only main products were isolated in the reaction. The structures of the spiro compounds 4a~4l were characterized by various spectroscopies. Because there are three chiral carbon atoms in the products, and several diastereoisomers might be produced in the reaction. ¹H NMR and ¹³C NMR spectra clearly showed that only one diastereoisomer exists in the products 4a~4l. For determining the relative configuration, the single crystal structures of compounds 4d (Figure 5) and 4e were successfully determined by X-ray diffraction. From the two figures, it can be seen that the same relative configuration was observed in the two molecules. Phenyl group and benzoyl group existed on trans-position. The one proton at the bridged carbon atom exists on the cis-position of phenyl group. Thus, on the basis of NMR spectra and single crystal data, it could be concluded that all compounds 4a~4l have the trans-configuration.

Table 3

Table 3. Synthesis of spiro[indene-2, 3'-pyrrolo[1, 2-a]quino-line]s 4a~4l^a

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Entry	Compd.	Ar	Ar	Yield^b/%
1	4a	C₆H₅	p-CH₃C₆H₄	76
2	4b	C₆H₅	m-ClC₆H₄	76
3	4c	C₆H₅	p-BrC₆H₄	78
4	4d	C₆H₅	m-NO₂C₆H₄	74
5	4e	p-CH₃OC₆H₄	m-CH₃OC₆H₄	90
6	4f	p-ClC₆H₄	C₆H₅	71
7	4g	p-ClC₆H₄	p-CH₃C₆H₄	75
8	4h	p-ClC₆H₄	m-CH₃C₆H₄	75
9	4i	p-ClC₆H₄	m-ClC₆H₄	78
10	4j	p-ClC₆H₄	p-ClC₆H₄	70
11	4k	p-ClC₆H₄	p-BrC₆H₄	75
12	4l	p-ClC₆H₄	m-O₂NC₆H₄	78
^a Reaction conditions: quinolinium salt (0.6 mmol), aromatic aldehyde (0.5 mmol), 1, 3-indanedione (0.5 mmol), Et₃N (0.5 mmol), EtOH (10.0 mL); r.t., 5 h. ^b Isolated yield.

Figure 5

Figure 5. Single crystal structure of compound 4d

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For demonstrating the synthetic values of this reaction, N-ethoxycarbonylmentyl- and N-(p-nitrobenzyl)quino- linium bromides were also employed to react with 2- aryl- idene-1, 3-indanediones at the same reactions. The corres- ponding spiro[indene-2, 3'-pyrrolo[1, 2-a]quinoline]s 5a~5g were successfully obtained in high yields (Table 4). The chemical structures of spiro compounds were established on the various spectroscopy. The single crystal structure of the compound 5a was also determined (Figure 6). We were pleased to find that it has same trans-configuration as that of the above spiro compounds 4d and 4e, in which the phenyl group and ethoxycarbonyl group exist on the trans-position. This result clearly indicated that the cycloaddition reaction of various quinolinium ylides with 2-arylidene-1, 3-indanediones has same outcome of stereochemistry and high diastereoselectivity.

Table 4

Table 4. Synthesis of spiro[indene-2, 3'-pyrrolo[1, 2-a]quinoli-ne]s 5a~5g^a

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Compd.	EWG	Ar	Yield^b/%
5a	CO₂C₂H₅	C₆H₅	65
5b	CO₂C₂H₅	m-CH₃C₆H₄	71
5c	CO₂C₂H₅	p-CH₃C₆H₄	58
5d	CO₂C₂H₅	m-CH₃OC₆H₄	64
5e	CO₂C₂H₅	m-ClC₆H₄	65
5f	p-O₂NC₆H₄	m-ClC₆H₄	79
5g	p-O₂NC₆H₄	m-CH₃C₆H₄	75
^a Reaction conditions: quinolinium salt (0.6 mmol), aromatic aldehyde (0.5 mmol), 1, 3-indanedione (0.5 mmol), Et₃N (0.5 mmol), EtOH (10.0 mL); r.t., 5 h. ^b Isolated yield.

Figure 6

Figure 6. Single crystal structure of the compound 5a

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3. Conclusions

In summary, we investigated the base promoted cycloaddition reaction of various quinolinium bromides with 1, 3-indanedione and 2-arylidene-1, 3-indanediones. The reaction showed very interesting molecular diversity and diastereoselectivty. The several indanone-containing hete- rocycles such as functionalized dihydropyrrolo[1, 2-a]-quinolines, 2-(1-(2-oxo-2-phenylethyl)-quinolin-4-ylide- ne)-indene-1, 3-diones and spiro[indene-2, 3'-pyrrolo[1, 2- a]quinoline]s were conveniently and selectively synthesized. A plausible reaction mechanism was rationally proposed to explain the formation of different kinds of products. The stereochemistry of the compounds were clearly elucidated by determination of ten single crystal structures. This reaction not only provided efficient method for preparing diverse indanone-containing heterocycles, but also developed the synthetic applications of quinolinium ylides in organic reactions.

4. Experimental section

4.1 General procedure for the reaction of N-phena- cylquinolinium salts with 1, 3-indanedione

To a round flask were added N-phenacylquinolinium bromide (1.2 mmol), 1, 3-indanedione (0.5 mmol), ethanol (15.0 mL) and triethylamine (1.5 mmol). The mixture was stirred at room temperature for 4 h. The solvent was removed at reduced pressure by rotatory evaporation. The resulting residue was subjected to column chromatography with petroleum and ethyl acetate (V:V＝2:1) as eluent to give products 1a~1f and 2a~2f.

N-(2-(1-Benzoyl-3-((1, 3-dioxo-1, 3-dihydro-2H-inden-2-ylidene)methyl)-1, 2-dihydropyrrolo[1, 2-a]quinolin-2-yl)-phenyl)benzamide (1a): Yield 59%. Purple solid, m.p. 199~201 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.49 (d, J＝9.3 Hz, 1H, ArH), 8.26~8.18 (m, 3H, ArH), 8.06 (d, J＝7.7 Hz, 1H, ArH), 8.00 (d, J＝7.5 Hz, 2H, ArH), 7.82 (s, 1H, ArH), 7.70 (t, J＝7.4 Hz, 1H, ArH), 7.66~7.55 (m, 4H, ArH), 7.55~7.46 (m, 6H, ArH), 7.43 (d, J＝8.6 Hz, 1H, ArH), 7.29 (s, 1H, ArH), 7.05 (t, J＝7.3 Hz, 1H, ArH), 6.85 (d, J＝7.3 Hz, 1H, ArH), 6.80 (s, 1H, CH), 6.75 (d, J＝8.1 Hz, 1H), 6.52 (t, J＝7.4 Hz, 1H, CH), 6.02 (s, 1H, CH), 5.41 (s, 1H, CH), 4.66 (d, J＝4.0 Hz, 2H, CH); ¹³C NMR (150 MHz, CDCl₃) δ: 194.6, 192.3, 191.9, 190.1, 158.8, 144.7, 139.5, 137.5, 135.3, 134.6, 133.6, 133.5, 133.0, 132.6, 132.4, 132.2, 130.0, 129.3, 128.8, 128.4, 127.7, 125.5, 125.0, 120.8, 120.7, 120.6, 118.5, 115.7, 114.5, 113.1, 112.4, 73.4, 50.3; IR (KBr) v: 3061, 2921, 1964, 1713, 1623, 1587, 1520, 1444, 1367, 1226, 1126, 1054, 970, 884, 818, 770, 700 cm^－1. HRMS (ESI) calcd for C₄₃H₃₁N₂O₄ [M+H]⁺ 639.2278; found 639.2289.

2-(1-(2-Oxo-2-phenylethyl)quinolin-4(1H)-ylidene)-1H- indene-1, 3(2H)-dione (2a): Yield 12%. Orange solid, m.p. 224~226 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.56 (d, J＝7.2 Hz, 1H, ＝CH), 8.52 (d, J＝8.8 Hz, 1H, ArH), 8.34 (d, J＝6.8 Hz, 1H, ＝CH), 8.15 (d, J＝7.6 Hz, 2H, ArH), 7.87~7.86 (m, 2H, ArH), 7.82~7.78 (m, 1H, ArH), 7.69~7.65 (m, 2H, ArH), 7.62~7.56 (m, 5H, ArH), 6.52 (s, 2H, CH); ¹³C NMR (100 MHz, DMSO-d₆) δ: 192.6, 189.4, 153.5, 144.7, 139.7, 139.5, 134.9, 134.4, 133.8, 132.5, 129.4, 129.3, 128.9, 128.8, 124.7, 124.5, 123.9, 120.4, 120.2, 117.4, 115.1, 107.5, 60.6; IR (KBr) v: 3053, 2916, 1797, 1709, 1623, 1579, 1517, 1483, 1415, 1344, 1237, 1173, 1091, 1019, 957, 874, 811, 739 cm^－1. HRMS (ESI) calcd for C₂₆H₁₇NNaO₃ [M+Na]⁺ 414.1101; found 414.1133.

2-((1-(4-Methylbenzoyl)-2-(2-((2-oxo-2-(p-tolyl)ethyl)-amino)phenyl)-1, 2-dihydropyrrolo[1, 2-a]quinolin-3-yl)me- thylene)-1H-indene-1, 3(2H)-dione (1b): Yield 61%. Purple solid, m.p. 208~210 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.48 (d, J＝10.0 Hz, 1H, ArH), 8.20 (d, J＝9.2 Hz, 1H, ArH), 8.10~8.04 (m, 3H, ArH), 7.90 (d, J＝7.2 Hz, 2H, ArH), 7.82 (s, 1H, ArH), 7.64~7.60 (m, 1H, ArH), 7.49~7.46 (m, 4H, ArH), 7.42~7.35 (m, 3H, ArH), 7.30~7.24 (m, 3H, ArH), 7.07~7.04 (m, 1H, ArH), 6.85 (d, J＝7.2 Hz, 1H, ArH), 6.78 (d, J＝8.4 Hz, 1H, ArH), 6.71~6.70 (m, 1H, ArH), 6.54~6.50 (m, 1H, ArH), 5.96 (s, 1H, CH), 5.36 (brs, 1H, CH), 4.60 (s, 2H, CH), 2.43 (s, 3H, CH₃), 2.17 (s, 3H, CH₃); ¹³C NMR (150 MHz, CDCl₃) δ: 194.0, 192.4, 145.5, 144.6, 143.9, 141.3, 136.7, 133.0, 132.3, 130.0, 129.9, 129.4, 129.3, 129.2, 129.0, 128.6, 128.0, 127.8, 125.7, 125.5, 122.1, 120.0, 117.3, 115.7, 115.5, 115.1, 112.7, 110.5, 73.0, 49.7, 45.7, 21.2, 21.1, 8.5; IR (KBr) v: 3042, 2919, 2838, 1955, 1723, 1646, 1475 1445, 1337, 1269, 114, 1074, 1008, 917, 846, 823, 709 cm^－1. HRMS (ESI) calcd for C₄₅H₃₄N₂NaO₄ [M+Na]⁺ 689.2411; found 689.2451.

2-(1-(2-Oxo-2-(p-tolyl)ethyl)quinolin-4(1H)-ylidene)-1H-indene-1, 3(2H)-dione (2b): Yield 13%. Orange solid, m.p. 223~225 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.55~8.50 (m, 2H, ArH, ＝CH), 8.33 (d, J＝6.8 Hz, 1H, ＝CH), 8.05 (d, J＝8.0 Hz, 2H, ArH), 7.89~7.81 (m, 2H, ArH), 7.62~7.56 (m, 5H, ArH), 7.48 (d, J＝8.0 Hz, 2H, ArH), 6.46 (s, 2H, CH), 2.46 (s, 3H, CH₃); ¹³C NMR (100 MHz, DMSO-d₆) δ: 192.0, 189.4, 153.5, 145.6, 144.7, 139.7, 139.5, 133.8, 132.5, 131.9, 130.0, 129.9, 128.9, 128.8, 124.5, 123.9, 120.2, 117.3, 117.3, 115.0, 107.5, 60.4, 21.8; IR (KBr) v: 3047, 2920, 1788, 1724, 1633, 1586, 1524, 1491, 1420, 1339, 1242, 1180, 1089, 1025, 961, 869, 814, 742 cm^－1. HRMS (ESI) calcd for C₂₇H₁₉- NNaO₃ [M+Na]⁺ 428.1257; found 428.1289.

2-((1-(4-Chlorobenzoyl)-2-(2-((2-(4-chlorophenyl)-2-oxoethyl)amino)phenyl)-1, 2-dihydropyrrolo[1, 2-a]quino-lin-3-yl)methylene)-1H-indene-1, 3(2H)-dione (1c): Yield 65%. Purple solid, m.p. 210~212 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.56~8.44 (m, 2H, ArH), 8.32~8.28 (m, 1H, ArH), 8.27~8.22 (m, 1H, ArH), 8.21~8.17 (m, 1H, ArH), 8.16~8.12 (m, 1H, ArH), 8.09~8.01 (m, 2H, ArH), 7.84 (d, J＝14.4 Hz, 2H, ArH), 7.77~7.71 (m, 1H, ArH), 7.70~7.65 (m, 1H, ArH), 7.62 (d, J＝18.0 Hz, 2H, ArH), 7.54 (d, J＝7.9 Hz, 1H, ArH), 7.49 (s, 2H, ArH), 7.40 (d, J＝8.2 Hz, 1H, ArH), 7.27~7.26 (m, 1H, ArH), 7.09~7.03 (m, 1H, ArH), 6.83~6.78 (m, 1H, ArH), 6.46 (s, 1H, CH), 6.57~6.50 (m, 1H, CH), 6.46 (s, 1H, CH), 5.98 (s, 1H, CH), 5.46~5.40 (m, 1H, CH), 4.66 (d, J＝0.9 Hz, 2H, CH); ¹³C NMR (150 MHz, CDCl₃) δ: 191.3, 189.1, 153.2, 144.2, 139.4, 139.3, 139.1, 133.5, 132.6, 132.4, 132.2, 132.1, 131.8, 130.3, 129.7, 129.1, 128.9, 128.1, 124.3, 123.5, 120.0, 116.9, 114.7, 107.1, 60.1, 54.8, 18.5; IR (KBr) v: 3063, 2924, 2858, 1965, 1717, 1651, 1487, 1448, 1333, 1273, 1165, 1084, 1017, 920, 864, 802, 707 cm^－1. HRMS (ESI) calcd for C₄₃H₂₉Cl₂N₂O₄ [M+H]⁺ 707.1499; found 707.1499.

2-((1-(4-Bromobenzoyl)-2-(2-((2-(4-bromophenyl)-2-oxoethyl)amino)phenyl)-1, 2-dihydropyrrolo[1, 2-a]quino-lin-3-yl)methylene)-1H-indene-1, 3(2H)-dione (1d): Yield 58%. Purple solid, m.p. 214~216 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.47 (d, J＝8.8 Hz, 1H, ArH), 8.22~8.16 (m, 3H, ArH), 8.05 (d, J＝8.0 Hz, 1H, ArH), 7.99 (d, J＝7.6 Hz, 2H, ArH), 7.84~7.82 (m, 3H, ArH), 7.72~7.70 (m, 2H, ArH), 7.66~7.62 (m, 1H, ArH), 7.51~7.41 (m, 5H, ArH), 7.28~7.26 (m, 1H, ArH), 7.08~7.04 (m, 1H, ArH), 6.85~6.76 (m, 3H, ArH), 6.56~6.52 (m, 1H, CH), 6.01 (s, 1H, CH), 5.46 (brs, 1H, CH), 4.69~4.65 (m, 2H, CH); ¹³C NMR (150 MHz, CDCl₃) δ: 194.1, 192.3, 190.3, 188.6, 158.8, 144.4, 141.4, 140.8, 138.8, 136.7, 133.7, 133.1, 132.6, 132.3, 132.1, 132.0, 131.8, 131.6, 131.3, 131.2, 129.8, 129.4, 128.1, 127.7, 125.7, 125.4, 120.0, 117.7, 115.7, 115.4, 112.8, 110.6, 73.2, 56.0, 49.9, 45.7, 18.5, 8.5; IR (KBr) v: 3059, 2937, 2846, 1959, 1727, 1647, 1498, 1463, 1327, 1279, 1153, 1057, 1009, 917, 856, 811, 703 cm^－1. HRMS (ESI) calcd for C₄₃H₂₉Br₂N₂O₄ [M+H]⁺ 795.0489; found 795.0524.

2-(1-(2-(4-Bromophenyl)-2-oxoethyl)quinolin-4(1H)-yl-idene)-1H-indene-1, 3(2H)-dione (2d): Yield 14%. Orange solid, m.p. 232~234 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.52~8.47 (m, 2H, ArH, ＝CH), 8.30 (d, J＝7.2 Hz, 1H, ＝CH), 8.11 (d, J＝7.6 Hz, 2H, ArH), 7.83~7.82 (m, 2H, ArH), 7.78~7.74 (m, 1H, ArH), 7.66~7.62 (m, 2H, ArH), 7.59~7.53 (m, 4H, ArH), 6.47 (s, 2H, CH); ¹³C NMR (100 MHz, DMSO-d₆) δ: 192.5, 189.4, 153.6, 144.6, 139.7, 139.5, 134.9, 134.4, 133.9, 132.5, 129.4, 128.8, 124.6, 123.9, 120.3, 117.3, 115.0, 107.5, 60.6; IR (KBr) v: 3051, 2917, 1774, 1733, 1641, 1595, 1536, 1487, 1419, 1344, 1238, 1176, 1092, 1018, 959, 872, 809, 750 cm^－1. HRMS (ESI) calcd for C₂₆H₁₆BrNNaO₃ [M+Na]⁺ 492.0306; found 492.0297.

Methyl 3-((1, 3-dioxo-1, 3-dihydro-2H-inden-2-ylidene)- methyl)-2-(2-((methoxycarbonyl)amino)phenyl)-1, 2-dihy-dropyrrolo[1, 2-a]quinoline-1-carboxylate (1e): Yield 57%. Red solid, m.p. 218~220 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.36 (d, J＝9.2 Hz, 1H, ArH), 8.13 (d, J＝8.8 Hz, 1H, ArH), 8.00~7.93 (m, 2H, ArH), 7.74~7.69 (m, 1H, ArH), 7.56 (s, 3H, ArH), 7.51~7.43 (m, 3H, ArH), 7.01~6.98 (m, 1H, ArH), 6.73 (d, J＝7.2 Hz, 1H, ArH), 6.66 (d, J＝8.0 Hz, 1H, ArH), 6.43 (t, J＝6.8 Hz, 1H, CH), 6.01 (s, 1H, CH), 5.71 (s, 1H, CH), 5.45~5.43 (m, 1H, CH), 4.26 (s, 2H, CH), 3.88 (s, 3H, OCH₃), 3.78 (s, 3H, OCH₃); ¹³C NMR (150 MHz, DMSO-d₆) δ: 190.8, 189.5, 188.8, 172.1, 169.5, 168.2, 158.2, 153.7, 145.1, 144.6, 139.7, 139.2, 137.5, 134.1, 132.7, 132.7, 125.9, 125.4, 124.8, 123.7, 120.5, 116.9, 114.8, 112.4, 111.8, 107.8, 54.3, 53.3, 52.4; IR (KBr) v: 3041, 2923, 1717, 1654, 1605, 1490, 1340, 1276, 1174, 1087, 1022, 912, 813, 746, 703 cm^－1. HRMS (ESI) calcd for C₃₃H₂₆N₂NaO₆ [M+Na]⁺ 569.1683; found 569.1678

Ethyl 3-((1, 3-dioxo-1, 3-dihydro-2H-inden-2-ylidene)- methyl)-2-(2-((2-ethoxy-2-oxoethyl)amino)phenyl)-1, 2-di- hydropyrrolo[1, 2-a]quinoline-1-carboxylate (1f): Yield 63%. Red solid, m.p. 226~228 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.32 (d, J＝9.2 Hz, 1H, ＝CH), 8.09 (d, J＝9.2 Hz, 1H, ＝CH), 7.94 (d, J＝7.2 Hz, 1H, ArH), 7.89 (s, 1H, ＝CH), 7.71~7.67 (m, 1H, ArH), 7.52 (s, 3H, ArH), 7.46~7.41 (m, 3H, ArH), 6.98~6.94 (m, 1H, ArH), 6.70 (d, J＝7.2 Hz, 1H, ArH), 6.63 (d, J＝8.0 Hz, 1H, ArH), 6.42~6.38 (m, H, CH), 6.00 (s, 1H, CH), 5.72 (s, 1H, CH), 5.67 (s, 1H, CH), 4.43~4.40 (m, 1H, CH), 4.23~4.17 (m, 4H, CH), 1.23(t, J＝7.2 Hz, 3H, CH₃); ¹³C NMR (100 MHz, DMSO-d₆) δ:190.8, 188.8, 171.6, 168.8, 158.1, 145.2, 141.5, 141.2, 139.5, 137.4, 133.3, 130.0, 129.8, 128.3, 126.1, 125.9, 125.3, 120.5, 117.2, 116.0, 115.7, 115.5, 112.5, 111.8, 111.7, 69.7, 69.7, 63.2, 61.0, 55.3, 46.1, 14.5; IR (KBr) v: 3052, 2917, 1713, 1659, 1614, 1478, 1353, 1278, 1194, 1078, 1005, 922, 809, 757, 707 cm^－1. HRMS (ESI) calcd for C₃₅H₃₀N₂NaO₆ [M+Na]⁺ 597.1996; found 597.2037

Ethyl 2-(4-(1, 3-dioxo-1, 3-dihydro-2H-inden-2-ylidene)- quinolin-1(4H)-yl)acetate (2f): Yield 10%. Orange solid, m.p. 229~231 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.55~8.49 (m, 2H, ArH, ＝CH), 8.31 (d, J＝7.2 Hz, 1H, ＝CH), 7.96~7.92 m, 1H, ArH), 7.86~7.84 (m, 1H, ArH), 7.61~7.58 (m, 5H, ArH), 5.64 (s, 2H, CH), 4.25~4.20 (m, 2H, CH), 1.24 (t, J＝6.8 Hz, 3H, CH₃); ¹³C NMR (100 MHz, DMSO-d₆) δ: 189.4, 189.3, 167.7, 167.6, 153.6, 144.5, 139.7, 139.1, 134.0, 132.6, 124.7, 124.6, 123.7, 120.3, 116.8, 114.7, 107.7, 62.2, 55.0, 14.4, 14.3; IR (KBr) v: 3061, 2923, 1768, 1727, 1637, 1587 1540, 1477, 1425, 1331, 1241, 1177, 1089, 1026, 962, 881, 813, 748 cm^－1. HRMS (ESI) calcd for C₂₂H₁₇NNaO₄ [M+Na]⁺ 382.1050; found 382.1076.

4.2 General procedure for the reaction of N-ben- zylquinolinium salts with 1, 3-indanedione

To a round flask were added N-benzylquinolinium bromide (0.5 mmol), 1, 3-indanedione (0.5 mmol), ethanol (15.0 mL) and triethylamine (1.0 mmol). The mixture was stirred at room temperature for 4 h. The solvent was removed at reduced pressure by rotatory evaporation. The resulting residue was subjected to column chromatography with a petroleum and ethyl acetate (V:V＝2:1) as eluent to give products 3a~3o.

2-(1-Benzylquinolin-4(1H)-ylidene)-1H-indene-1, 3-(2H)-dione (3a): Yield 68%. Orange solid, m.p. 239~241 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.85 (d, J＝7.2 Hz, 1H, ＝CH), 8.49 (d, J＝8.4 Hz, 1H, ArH), 8.38 (d, J＝7.2 Hz, 1H, ＝CH), 7.98 (d, J＝8.8 Hz, 1H, ArH), 7.88~7.84 (m, 1H, ArH), 7.59~7.53 (m, 5H, ArH), 7.39~7.35 (m, 2H, ArH), 7.32~7.28 (m, 3H, ArH), 5.93 (s, 2H, CH); ¹³C NMR (100 MHz, DMSO-d₆) δ: 189.4, 153.5, 144.6, 139.8, 138.6, 135.9, 133.9, 132.8, 132.6, 129.4, 128.6, 127.1, 124.8, 124.4, 120.4, 117.7, 115.2, 107.5, 57.5; IR (KBr) v: 3063, 2926, 1790, 1717, 1630, 1586, 1526, 1485, 1408, 1336, 1245, 1166, 1086, 1013, 967, 884, 817, 746 cm^－1. HRMS (ESI) calcd for C₂₅H₁₈- NO₂ [M+H]⁺ 364.1332; found 364.1336.

2-(1-(4-Methoxybenzyl)quinolin-4(1H)-ylidene)-1H-indene-1, 3(2H)-dione (3b): Yield 72%. Orange solid, m.p. 228~230 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.84 (d, J＝7.6 Hz, 1H, ＝CH), 8.47 (d, J＝8.4 Hz, 1H, ArH), 8.35 (d, J＝7.2 Hz, 1H, ＝CH), 8.05 (d, J＝8.8 Hz, 1H, ArH), 7.89~7.85 (m, 1H, ArH), 7.60~7.53 (m, 5H, ArH), 7.29 (d, J＝8.8 Hz, 2H, ArH), 6.92 (d, J＝8.8 Hz, 2H, CH), 5.84 (s, 2H, CH), 3.70 (s, 3H, OCH₃); ¹³C NMR (100 MHz, DMSO-d₆) δ: 190.8, 159.9, 154.1, 141.3, 139.8, 138.7, 133.4, 133.3, 132.2, 128.0, 125.5, 124.6, 124.4, 120.5, 115. 9, 115.1, 114.7, 109.0, 57.7, 55.3; IR (KBr) v: 3060, 1966, 1713, 1643, 1482, 1435, 1330, 1292, 1237, 1179, 1079, 1016, 913, 852, 807, 711 cm^－1. HRMS (ESI) calcd for C₂₆H₂₀NO₃ [M+H]⁺ 394.1438; found 394.1436.

2-(1-(4-Methylbenzyl)quinolin-4(1H)-ylidene)-1H-indene-1, 3(2H)-dione (3c): Yield 71%. Orange solid, m.p. 224~226 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.84 (d, J＝7.2 Hz, 1H, ＝CH), 8.48 (d, J＝9.6 Hz, 1H, ArH), 8.36 (d, J＝6.8 Hz, 1H, ＝CH), 7.98 (d, J＝8.8 Hz, 1H, ArH), 7.88~7.84 (m, 1H, ArH), 7.61~7.52 (m, 5H, ArH), 7.21~7.16 (m, 4H, ArH), 5.87 (s, 2H, CH), 2.25 (s, 3H, CH₃); ¹³C NMR (100 MHz, DMSO-d₆) δ: 189.3, 153.4, 144.5, 139.7, 138.5, 137.9, 133.9, 133.8, 132.8, 132.7, 132.5, 129.9, 127.1, 124.7, 124.4, 120.3, 117.7, 115.2, 107.3, 57.3, 21.1, 21.0; IR (KBr) v: 3053, 1986, 1731, 1635, 1458, 1435, 1303, 1298, 1259, 1167, 1056, 1018, 925, 858, 807, 716 cm^－1. HRMS (ESI) calcd for C₂₆H₂₀- NO₂ [M+H]⁺ 378.1489; found 378.1478.

2-(1-(4-(tert-Butyl)benzyl)quinolin-4(1H)-ylidene)-1H-indene-1, 3(2H)-dione (3d): Yield 87%. Orange solid, m.p. 232~234 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.84 (d, J＝8.4 Hz, 1H, ＝CH), 8.48 (d, J＝8.0 Hz, 1H, ArH), 8.36 (d, J＝8.4 Hz, 1H, ＝CH), 8.04~8.02 (m, 1H, ArH), 7.90~7.87 (m, 1H, ArH), 7.59~7.54 (m, 5H, ArH), 7.39~7.38 (m, 2H, ArH), 7.24~7.22 (m, 2H, ArH), 5.89 (s, 2H, CH), 1.22 (s, 9H, C(CH₃)₃).; ¹³C NMR (100 MHz, DMSO-d₆) δ: 189.3, 153.4, 151.0, 144.5, 139.7, 138.6, 133.9, 133.9, 132.8, 132.7, 126.9, 126.2, 126.1, 124.3, 120.4, 117.7, 115.1, 107.3, 57.1, 34.6, 31.4, 31.3; IR (KBr) v: 3025, 2887, 1764, 1735, 1654, 1576, 1458, 1347, 1272, 1187, 1094, 1023, 905, 848, 764, 706 cm^－1. HRMS (ESI) calcd for C₂₉H₂₅NNaO₂ [M+Na]⁺ 442.1778; found 442.1779.

2-(1-(3, 5-Dimethoxybenzyl)quinolin-4(1H)-ylidene)-1H-indene-1, 3(2H)-dione (3e): Yield 76%. Orange solid, m.p. 236~238 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.80 (d, J＝7.2 Hz, 1H, ＝CH), 8.49 (d, J＝8.8 Hz, 1H, ArH), 8.36 (d, J＝6.4 Hz, 1H, ＝CH), 8.01~7.99 (m, 1H, ArH), 7.90~7.87 (m, 1H, ArH), 7.58~7.53 (m, 5H, ArH), 6.44 (s, 3H, ArH), 5.82 (s, 2H, CH), 3.70 (s, 6H, OCH₃); ¹³C NMR (100 MHz, DMSO-d₆) δ: 189.3, 161.3, 153.4, 144.5, 139.7, 138.6, 138.1, 133.8, 132.7, 132.5, 124.8, 124.2, 120.4, 120.2, 117.6, 115.0, 107.4, 105.6, 105.4, 99.6, 99.5, 57.4, 55.7, 55.6. HRMS (ESI) calcd for C₂₇H₂₁NNaO₄ [M+Na]⁺ 446.1363; found 446.1356.

2-(1-(4-Chlorobenzyl)quinolin-4(1H)-ylidene)-1H-in-dene-1, 3(2H)-dione (3f): Yield 75%. Orange solid, m.p. 216~218 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.82 (d, J＝7.2 Hz, 1H, ＝CH), 8.50 (d, J＝8.4Hz, 1H, ArH), 8.37 (d, J＝7.2 Hz, 1H, ＝CH), 7.94 (d, J＝8.8 Hz, 1H, ArH), 7.89~7.85 (m, 1H, ArH), 7.61~7.53 (m, 5H, ArH), 7.44 (d, J＝8.8 Hz, 2H, ArH), 7.32 (d, J＝8.4 Hz, 2H, CH), 5.92 (s, 2H, CH); ¹³C NMR (100 MHz, DMSO-d₆) δ: 194.2, 158.2, 149.3, 144.5, 143.3, 139.7, 138.7, 138.0, 137.6, 137.4, 137.3, 134.7, 134.2, 133.8, 131.9, 129.6, 129.1, 125.2, 125.1, 122.3, 119.9, 112.3, 61.5, 25.8; IR (KBr) v: 3065, 2922, 2855, 1718, 1652, 1589, 1488, 1439, 1335, 1284, 1182, 1134, 1089, 1011, 920, 821, 755, 710 cm^－1. HRMS (ESI) calcd for C₂₅H₁₇ClNO₂ [M+H]⁺ 398.0942; found 398.0929.

2-(1-(3-Chlorobenzyl)quinolin-4(1H)-ylidene)-1H-inde-ne-1, 3(2H)-dione (3g): Yield 78%. Orange solid, m.p. 214~216 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.82 (d, J＝6.8 Hz, 1H, ＝CH), 8.50 (d, J＝8.4 Hz, 1H, ArH), 8.38 (d, J＝6.8 Hz, 1H, ＝CH), 7.98~7.95 (m, 1H, ArH), 7.90~7.86 (m, 1H, ArH), 7.59~7.54 (m, 5H, ArH, CH), 7.47 (d, J＝7.6 Hz, 2H, ArH), 6.04 (s, 2H, CH); ¹³C NMR (100 MHz, DMSO-d₆) δ: 189.4, 153.4, 144.6, 139.7, 138.5, 138.3, 134.0, 132.8, 132.6, 131.3, 128.6, 127.2, 127.1, 125.6, 124.8, 124.2, 120.5, 120.3, 117.5, 115.1, 107.6, 56.7; IR (KBr) v: 3051, 2894, 1758, 1718, 1645, 1576, 1488, 1353, 1272, 1174, 1084, 1018, 925, 843, 757, 716 cm^－1. HRMS (ESI) calcd for C₂₅H₁₆ClNNaO₂ [M+Na]⁺ 420.0762; found 420.0760.

2-(1-(4-Bromobenzyl)quinolin-4(1H)-ylidene)-1H-inde-ne-1, 3(2H)-dione (3h): Yield 73%. Orange solid, m.p. 222~224 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.82 (d, J＝6.4 Hz, 1H, ＝CH), 8.50 (d, J＝7.6 Hz, 1H, ArH), 8.37 (d, J＝6.8 Hz, 1H, ＝CH), 7.95~7.85 (m, 2H, ArH), 7.59~7.57 (m, 7H, ArH, CH), 7.26 (d, J＝7.6 Hz, 2H, ArH), 5.90 (s, 2H, CH); ¹³C NMR (150 MHz, DMSO-d₆) δ: 188.9, 153.0, 144.0, 139.2, 138.0, 134.8, 133.5, 132.3, 132.1, 131.8, 128.9, 124.3, 123.8, 121.2, 119.9, 117.1, 114.6, 107.0, 56.3. HRMS (ESI) calcd for C₂₅H₁₆BrNNaO₂ [M+Na]⁺ 464.0257; found 464.0253.

2-(1-(4-(Trifluoromethyl)benzyl)quinolin-4(1H)-ylide-ne)-1H-indene-1, 3(2H)-dione (3i): Yield 75%. Orange solid, m.p. 218~220 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.83 (d, J＝6.4 Hz, 1H, ArH), 8.51 (d, J＝8.4 Hz, 1H, ArH), 8.40 (d, J＝6.8 Hz, 1H, ArH), 7.91~7.84 (m, 2H, ArH), 7.75 (d, J＝8.0 Hz, 2H, ArH), 7.60~7.54 (m, 5H, ArH, CH), 7.47 (d, J＝7.6 Hz, 2H, ArH), 6.04 (s, 2H, CH); ¹³C NMR (100 MHz, DMSO-d₆) δ: 189.4, 153.5, 144.6, 144.5, 140.7, 139.7, 138.5, 134.0, 132.9, 132.8, 132.6, 127.8, 127.7, 126.3, 126.2, 124.8, 124.7, 124.2, 120.5, 120.3, 115.0, 107.6, 56.8. HRMS (ESI) calcd for C₂₆H₁₆- F₃NNaO₂ [M+Na]⁺ 454.1025; found 454.1021.

2-(1-(4-Nitrobenzyl)quinolin-4(1H)-ylidene)-1H-indene- 1, 3(2H)-dione (3j): Yield 77%. Orange solid, m.p. 241~243 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.83 (d, J＝6.4 Hz, 1H, ＝CH), 8.52 (d, J＝8.0 Hz, 1H, ArH), 8.41 (d, J＝6.4 Hz, 1H, ＝CH), 8.23 (d, J＝7.6 Hz, 2H, ArH), 7.86 (brs, 2H, ArH), 7.60~7.51 (m, 6H, ArH), 6.09 (s, 2H, CH); ¹³C NMR (100 MHz, DMSO-d₆) δ: 189.5, 153.6, 147.6, 144.7, 143.6, 139.7, 138. 6, 134.1, 132.9, 132.7, 128.3, 124.9, 124.6, 124.27, 120.5, 117. 5, 115.1, 107.8, 56.8, 55.4; IR (KBr) v: 3062, 2928, 2866, 1780, 1713, 1595, 1493, 1448, 1337, 1281, 1189, 1090, 1022, 919, 865, 804, 713 cm^－1. HRMS (ESI) calcd for C₂₅H₁₇N₂O₄ [M+H]⁺ 409.1183; found 409.1171.

2-(1-Butylquinolin-4(1H)-ylidene)-1H-indene-1, 3(2H)-dione (3k): Yield 70%. Orange solid, m.p. 211~213 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.66 (d, J＝6.8 Hz, 1H, ＝CH), 8.48 (d, J＝8.4 Hz, 1H, ArH), 8.25 (d, J＝6.8 Hz, 1H, ＝CH), 8.13 (d, J＝8.8 Hz, 1H, ArH), 7.99~7.95 (m, 1H, ArH), 7.62~7.55 (m, 5H, ArH, CH), 4.65 (t, J＝7.2 Hz, 2H, CH), 1.89~1.81 (m, 2H, CH), 1.41~1.32 (m, 2H, CH), 0.92 (t, J＝7.2 Hz, 3H, CH₃); ¹³C NMR (100 MHz, DMSO-d₆) δ: 189.3, 153.2, 144.1, 139.7, 138.4, 133.9, 132.8, 132.4, 124.8, 124.5, 120.2, 117.3, 115.4, 106.9, 54.6, 31.43, 19.71, 13.9; IR (KBr) v: 3069, 2924, 1785, 1718, 1654, 1590, 1482, 1333, 1277, 1172, 1088, 1011, 916, 820, 752, 706 cm^－1. HRMS (ESI) calcd for C₂₂H₂₀N- O₂ [M+H]⁺ 330.1489; found 330.1469.

2-(1-Benzyl-4-methylquinolin-2(1H)-ylidene)-1H-indene- 1, 3(2H)-dione (3l): Yield 72%. Orange solid, m.p. 230~232 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.20~8.18 (m, 2H, ArH), 8.10 (d, J＝8.0 Hz, 1H, ＝CH), 7.76~7.72 (m, 1H, ArH), 7.58 (s, 5H, ArH), 7.20~7.12 (m, 3H, ArH), 6.91 (d, J＝6.4 Hz, 2H, ArH), 6.06 (s, 2H, CH), 2.76 (s, 3H, CH₃); ¹³C NMR (150 MHz, DMSO-d₆) δ: 187.8, 154.7, 149.0, 138.9, 138.1, 136.4, 132.2, 131.9, 128.6, 127.4, 126.2, 126.0, 125.9, 124.3, 120.0, 119.8, 103.7, 56.8, 19.2. HRMS (ESI) calcd for C₂₆H₂₀NO₂ [M+H]⁺ 378.1489; found 378.1483.

2-(1-(4-Fluorobenzyl)-4-methylquinolin-2(1H)-ylidene)-1H-indene-1, 3(2H)-dione (3m): Yield 75%. Yellow solid, m.p. 285~287 ℃; ¹H NMR (600 MHz) δ: 8.37 (s, 1H, ArH), 7.92~7.89 (m, 1H, ＝CH), 7.73~7.69 (m, 3H, ArH), 7.57~7.54 (m, 3H, ArH), 7.47~7.45 (m, 1H, ArH), 6.86~6.84 (m, 4H, ArH), 5.93 (s, 2H, CH), 2.74 (s, 3H, CH₃); ¹³C NMR (150 MHz, CDCl₃) δ: 189.7, 162.8, 161.1, 155.6, 147.9, 139.5, 138.5, 132.3, 132.1, 132.1, 131.2, 128.0, 127.9, 126.6, 125.7, 125.3, 125.2, 120.6, 119.8, 115.9, 115.8, 104.8, 57.9, 19.6; IR (KBr) v: 3055, 1625, 1593, 1478, 1434, 1352, 1225, 1133, 1060, 955, 893, 866, 746 cm^－1. HRMS (ESI) calcd for C₂₆H₁₈FNNaO₂ [M+ Na]⁺ 418.1214; found 418.1216.

2-(1-(4-Chlorobenzyl)-4-methylquinolin-2(1H)-ylidene)- 1H-indene-1, 3(2H)-dione (3n): Yield 78%. Yellow solid, m.p. 288~290 ℃; ¹H NMR (600 MHz) δ: 8.37 (s, 1H, ArH), 7.92~7.89 (m, 1H, CH), 7.71~7.67 (m, 3H, ArH), 7.57~7.53 (m, 3H, ArH), 7.47~7.45 (m, 1H, ArH), 7.13~7.11 (m, 1H, ArH), 6.82~6.80 (m, 2H, ArH), 5.93 (s, 2H, CH), 2.74 (s, 3H, CH₃); ¹³C NMR (150 MHz, CDCl₃) δ: 189.7, 155.6, 147.9, 139.5, 138.4, 134.8, 133.5, 132.3, 131.3, 129.0, 127.6, 126.6, 125.7, 125.3, 125.1, 120.6, 119.7, 104.7, 57.9, 19.6; IR (KBr) v: 3687, 3055, 1625, 1590, 1481, 1436, 1353, 1332, 1174, 1131, 1086, 1015, 896, 871, 827, 745 cm^－1. HRMS (ESI) calcd for C₂₆H₁₈ClNNaO₂ [M+Na]⁺ 434.0918; found 434.0923.

2-(1-(4-Bromobenzyl)-4-methylquinolin-2(1H)-ylidene)- 1H-indene-1, 3(2H)-dione (3o): Yield 77%. Yellow solid, m.p. 281~283 ℃; ¹H NMR (600 MHz) δ: 8.37 (s, 1H, ArH), 7.92~7.90 (m, 1H, ＝CH), 7.71~7.69 (m, 3H, ArH), 7.57~7.54 (m, 3H, ArH), 7.48~7.45 (m, 1H, ArH), 6.76~6.74 (m, 2H, ArH), 5.91 (s, 2H, CH), 2.74 (s, 3H, CH₃); ¹³C NMR (150 MHz, CDCl₃) δ: 189.7, 155.6, 147.9, 139.5, 138.4, 135.4, 132.3, 131.9, 131.3, 127.9, 126.5, 125.7, 125.3, 125.1, 121.5, 120.6, 119.7, 104.7, 57.9, 19.6; IR (KBr) v: 3733, 3056, 1625, 1591, 1480, 1436, 1352, 1331, 1174, 1131, 1066, 1011, 895, 872, 810, 744 cm^－1. HRMS (ESI) calcd for C₂₆H₁₈BrNNaO₂ [M+Na]⁺ 478.0413; found 478.0418.

4.3 General procedure for the preparation of spiro[indene-2, 3'-pyrrolo[1, 2-a]quinoline]s 4a~4n and 5a~5g

To a 50 mL round flask were added N-penacylquino- linium bromide (0.6 mmol), aromatic aldehyde (0.5 mmol), 1, 3-indanedione (0.5 mmol), ethanol (10.0 mL) and triethylamine (1.0 mmol). The mixture was stirred at room temperature for 5 h. The resulting precipitates were collected by filtration. The crude product was stirred in ethanol (10.0 mL) at room temperature for 0.5 h to give the pure product after filtration.

1'-Benzoyl-2'-(p-tolyl)-1', 2'-dihydro-3a'H-spiro[indene- 2, 3'-pyrrolo[1, 2-a]quinoline]-1, 3-dione (4a): Yield 76%. Yellow solid, m.p. 152~156 ℃; ¹H NMR (600 MHz, CDCl₃) δ: 7.88~7.86 (m, 1H, ArH), 7.83~7.81 (m, 3H, ArH), 7.72~7.71 (m, 2H, ArH), 7.47 (t, J＝7.2 Hz, 1H, ArH), 7.29 (t, J＝7.2 Hz, 2H, ArH), 7.12 (d, J＝7.8 Hz, 2H, ArH), 6.93 (t, J＝7.2 Hz, 1H, ArH), 6.87 (d, J＝7.8 Hz, 2H, ArH), 6.77 (d, J＝7.2 Hz, 1H, ArH), 6.56 (t, J＝7.2 Hz, 1H, ArH), 6.26 (d, J＝10.2 Hz, 1H, CH), 6.07 (d, J＝8.4 Hz, 1H, CH), 5.77 (s, 1H, CH), 5.76 (s, 1H, CH), 4.97~4.95 (m, 1H, CH), 4.04 (d, J＝9.6 Hz, 1H, CH), 2.14 (s, 3H, CH₃); ¹³C NMR (150 MHz, CDCl₃) δ: 200.4, 199.3, 197.4, 143.2, 142.8, 142.5, 137.8, 135.8, 135.3, 133.4, 130.6, 130.0, 129.4, 128.0, 128.7, 128.5, 127.6, 123.1, 123.0, 119.2, 117.8, 116.6, 109.9, 71.2, 70.3, 70.1, 55.3, 20.9; IR (KBr) v: 1736, 1702, 1644, 1595, 1514, 1493, 1460, 1402, 1381, 1356, 1310, 1287, 1243, 1203, 1175, 1159, 1121, 1071, 1048, 1016, 975, 928, 865, 835, 804, 788, 762 cm^－1. HRMS (ESI) calcd for C₃₄H₂₅NNaO₃ [M+Na]⁺ 518.1727; found 518.1723.

1'-Benzoyl-2'-(3-chlorophenyl)-1', 2'-dihydro-3a'H-spiro-[indene-2, 3'-pyrrolo[1, 2-a]quinoline]-1, 3-dione (4b): Yield 76%. Yellow solid, m.p.184~186 ℃; ¹H NMR (600 MHz, CDCl₃) δ: 7.91~7.89 (m, 1H, ArH), 7.87~7.86 (m, 1H, ArH), 7.83 (d, J＝7.8 Hz, 2H, ArH), 7.77~7.76 (m, 2H, ArH), 7.50 (t, J＝7.8 Hz, 1H, ArH), 7.33 (t, J＝7.8 Hz, 2H, ArH), 7.22 (s, 1H, ArH), 7.18 (d, J＝6.6 Hz, 1H, ArH), 7.06~7.02 (m, 2H, ArH), 6.96 (t, J＝7.8 Hz, 1H, ArH), 6.80 (d, J＝7.2 Hz, 1H, ArH), 6.59 (t, J＝7.2 Hz, 1H, ArH), 6.27 (d, J＝10.2 Hz, 1H, ArH), 6.08 (d, J＝7.8 Hz, 1H, CH), 5.79 (t, J＝9.6 Hz, 1H, CH), 5.76 (s, 1H, CH), 4.97~4.95 (m, 1H, CH), 4.01 (d, J＝9.6 Hz, 1H, CH); ¹³C NMR (150 MHz, CDCl₃) δ: 200.0, 198.9, 197.0, 143.1, 142.4, 136.2, 136.0, 135.6, 135.3, 134.4, 133.6, 133.2, 132.7, 130.6, 130.2, 129.8, 129.5, 128.7, 128.6, 128.4, 127.7, 127.3, 123.2, 119.2, 118.1, 116.3, 109.9, 71.1, 70.5, 70.1, 54.9; IR (KBr) v: 1734, 1700, 1647, 1594, 1529, 1492, 1460, 1446, 1406, 1381, 1354, 1311, 1286, 1241, 1205, 1180, 1162, 1120, 1081, 1047, 1001, 976, 926, 895, 876, 850, 812, 775 cm^－1. HRMS (ESI) calcd for C₃₃H₂₂ClNNaO₃ [M+Na]⁺ 538.1180; found 538.1179.

1'-Benzoyl-2'-(4-bromophenyl)-1', 2'-dihydro-3a'H-spiro[indene-2, 3'-pyrrolo[1, 2-a]quinoline]-1, 3-dione (4c): Yield 78%. Yellow solid, m.p. 158~156 ℃; ¹H NMR (600 MHz, CDCl₃) δ: 7.89~7.88 (m, 1H, ArH), 7.85~7.82 (m, 3H, ArH), 7.77~7.75 (m, 2H, ArH), 7.51 (t, J＝7.2 Hz, 1H, ArH), 7.34 (t, J＝7.8 Hz, 2H, ArH), 7.21 (d, J＝8.4 Hz, 2H, ArH), 7.13 (d, J＝8.4 Hz, 2H, ArH), 6.95 (t, J＝7.8 Hz, 1H, ArH), 6.79 (d, J＝7.2 Hz, 1H, ArH), 6.59 (t, J＝7.2 Hz, 1H, ArH), 6.27 (d, J＝10.2 Hz, 1H, ArH), 6.08 (d, J＝7.8 Hz, 1H, CH), 5.77 (s, 1H, CH), 5.76 (brs, 1H, CH), 4.97~4.95 (m, 1H, CH), 4.03 (d, J＝9.6 Hz, 1H, CH); ¹³C NMR (150 MHz, CDCl₃) δ: 200.1, 198.1, 197.0, 143.1, 142.7, 136.1, 135.7, 135.2, 133.8, 133.1, 131.8, 130.9, 130.1, 129.5, 128.7, 128.6, 127.7, 123.2, 122.2, 119.2, 118.1, 116.4, 109.9, 77.1, 70.4, 70.1, 54.7; IR (KBr) v: 2905, 1735, 1701, 1644, 1594, 1491, 1460, 1402, 1381, 1356, 1310, 1284, 1264, 1242, 1207, 1175, 1158, 1121, 1073, 1049, 1010, 975, 927, 863, 833, 806, 791, 774 cm^－1. HRMS (ESI) calcd for C₃₃H₂₂BrNNaO₃ [M+Na]⁺ 582.0675; found 582.0662.

1'-Benzoyl-2'-(3-nitrophenyl)-1', 2'-dihydro-3a'H-spiro-[indene-2, 3'-pyrrolo[1, 2-a]quinoline]-1, 3-dione (4d): Yield 74%. Yellow solid, m.p.156~158 ℃; ¹H NMR (600 MHz, CDCl₃) δ: 8.10 (s, 1H, ArH), 7.94~7.90 (m, 2H, ArH), 7.85 (d, J＝7.2 Hz, 3H, ArH), 7.78~7.76 (m, 2H, ArH), 7.64 (d, J＝7.8 Hz, 1H, ArH), 7.49 (t, J＝7.2 Hz, 1H, ArH), 7.34~7.28 (m, 1H, ArH), 7.00 (t, J＝7.8 Hz, 1H, ArH), 6.80 (d, J＝7.2 Hz, 1H, ArH), 6.63 (t, J＝7.2 Hz, 1H, ArH), 6.29 (d, J＝10.2 Hz, 1H, ArH), 6.14 (d, J＝7.8 Hz, 1H, CH), 5.86 (d, J＝9.6 Hz, 1H, CH), 5.78 (s, 1H, CH), 4.97~4.95 (m, 1H, CH), 4.17 (d, J＝9.6 Hz, 1H, CH); ¹³C NMR (150 MHz, CDCl₃) δ: 199.7, 196.4, 148.0, 142.9, 142.5, 142.2, 136.3, 136.2, 135.8, 135.1, 133.8, 130.2, 129.6, 129.5, 128.7, 128.5, 127.7, 124.1, 123.3, 123.2, 119.0, 118.3, 116.0, 110.0, 71.1, 70.6, 70.1, 54.1; IR (KBr) v: 1771, 1736, 1701, 1652, 1595, 1533, 1492, 1459, 1406, 1351, 1313, 1242, 1205, 1164, 1048, 979, 855, 808, 777 cm^－1. HRMS (ESI) calcd for C₃₃H₂₂N₂NaO₅ [M+ Na]⁺ 549.1421; found 549.1407.

1'-(4-Methoxybenzoyl)-2'-(3-methoxyphenyl)-1', 2'-di-hydro-3a'H-spiro[indene-2, 3'-pyrrolo[1, 2-a]quinoline]-1, 3- dione (4e): Yield 90%. Yellow solid, m.p. 157~159 ℃; ¹H NMR (600 MHz, DMSO-d₆) δ: 7.96~7.95 (m, 1H, ArH), 7.92~7.90 (m, 4H, ArH), 7.85~7.84 (m, 1H, ArH), 7.03 (t, J＝7.8 Hz, 1H, ArH), 6.94~6.91 (m, 3H, ArH), 6.84 (d, J＝7.2 Hz, 1H, ArH), 6.76 (d, J＝7.8 Hz, 1H, ArH), 6.73 (brs, 1H, ArH), 6.66~6.65 (m, 1H, ArH), 6.53 (t, J＝7.2 Hz, 1H, ArH), 6.32 (d, J＝10.2 Hz, 1H, ArH), 6.00 (d, J＝8.4 Hz, 1H, CH), 5.86 (d, J＝9.0 Hz, 1H, CH), 5.62 (s, 1H, CH), 5.12 (dd, J＝9.6, 2.4 Hz, 1H, CH), 3.86 (d, J＝9.0 Hz, 1H, CH), 3.79 (s, 3H, OCH₃), 3.60 (s, 3H, OCH₃); ¹³C NMR (100 MHz, CDCl₃) δ: 199.3, 198.3, 197.3, 163.9, 159.5, 143.2, 142.8, 142.4, 135.8, 135.6, 135.3, 131.0, 130.0, 129.6, 129.4, 128.1, 127.5, 123.0, 122.9, 121.4, 119.2, 117.7, 116.6, 114.5, 114.0, 113.8, 109.8, 71.1, 70.4, 69.4, 55.9, 55.4, 55.1; IR (KBr) v: 3062, 2947, 2829, 1702, 1670, 1594, 1496, 1356, 1312, 1169, 974, 849, 783, 744 cm^－1. HRMS (ESI) calcd for C₃₅H₂₇N- O₅ [M+H]⁺ 542.1962; found 542.1977.

1'-(4-Chlorobenzoyl)-2'-phenyl-1', 2'-dihydro-3a'H-spiro-[indene-2, 3'-pyrrolo[1, 2-a]quinoline]-1, 3-dione (4f): Yield 71%. Yellow solid, m.p. 178~180 ℃; ¹H NMR (600 MHz, CDCl₃) δ: 7.90~7.87 (m, 1H, ArH), 7.84~7.83 (m, 2H, ArH), 7.74 (s, 1H, ArH), 7.75~7.72 (m, 4H, ArH), 7.27 (s, 1H, ArH), 7.25~7.24 (m, 3H, ArH), 7.10~7.09 (m, 3H, ArH), 6.94 (t, J＝7.8 Hz, 1H, ArH), 6.79 (d, J＝7.2 Hz, 1H, ArH), 6.58 (d, J＝7.8 Hz, 1H, ArH), 6.27 (d, J＝7.8 Hz, 1H, ArH), 6.00 (d, J＝8.4 Hz, 1H, CH), 5.76 (s, 1H, CH), 5.75 (d, J＝10.2 Hz, 1H, CH), 4.98~4.96 (m, 1H, CH), 4.03(d, J＝9.6 Hz, 1H, CH); ¹³C NMR (100 MHz, CDCl₃) δ: 199.4, 198.9, 197.0, 142.9, 142.6, 142.3, 140.0, 135.8, 135.3, 133.6, 133.3, 129.9, 129.3, 129.0, 128.7, 128.6, 128.2, 127.6, 123.0, 119.1, 117.9, 116.4, 109.6, 71.0, 70.1, 70.0, 55.4; IR (KBr) v: 2917, 1735, 1701, 1643, 1596, 1540, 1492, 1459, 1400, 1380, 1354, 1307, 1243, 1203, 1159, 1119, 1090, 1049, 1012, 975, 929, 868, 837, 811, 763 cm^－1. HRMS (ESI) calcd for C₃₃H₂₂Cl- NNaO₃ [M+Na]⁺ 538.1180; found 538.1173.

1'-(4-Chlorobenzoyl)-2'-(p-tolyl)-1', 2'-dihydro-3a'H-spi-ro[indene-2, 3'-pyrrolo[1, 2-a]quinoline]-1, 3-dione (4g): Yield 75%. Yellow solid, m.p.134~136 ℃; ¹H NMR (600 MHz, CDCl₃) δ: 7.88~7.87 (m, 1H, ArH), 7.85~7.83 (m, 1H, ArH), 7.76 (d, J＝8.4 Hz, 2H, ArH), 7.74~7.73 (m, 2H, ArH), 7.28 (d, J＝8.4 Hz, 2H, ArH), 7.12 (d, J＝8.4 Hz, 2H, ArH), 6.94 (t, J＝7.8 Hz, 1H, ArH), 6.90 (d, J＝7.8 Hz, 2H, ArH), 6.79 (d, J＝6.0 Hz, 1H, ArH), 6.58(t, J＝7.8 Hz, 1H, ArH), 6.26 (d, J＝10.2 Hz, 1H, ArH), 5.99 (d, J＝7.8 Hz, 1H, CH), 5.76 (brs, 1H, CH), 5.72 (d, J＝9.6 Hz, 1H, CH), 4.97~4.95 (m, 1H, CH), 4.01 (d, J＝9.6 Hz, 1H, CH), 2.16 (s, 3H, CH₃); ¹³C NMR (150 MHz, CDCl₃) δ: 199.2, 197.3, 143.2, 142.9, 142.5, 140.0, 138.0, 135.8, 135.4, 133.6, 130.6, 130.1, 129.4, 129.0, 127.7, 123.1, 123.0, 119.3, 118.0, 116.6, 109.9, 71.7, 70.3, 70.2, 55.3, 20.9; IR (KBr) v: 2909, 1736, 1700, 1648, 1593, 1514, 1491, 1460, 1403, 1381, 1355, 1311, 1272, 1250, 1203, 1163, 1119, 1090, 1048, 1012, 979, 926, 831, 817, 801, 776, 754 cm^－1. HRMS (ESI) calcd for C₃₄H₂₄ClNNaO₃ [M+Na]⁺ 552.1337; found 552.1321.

1'-(4-Chlorobenzoyl)-2'-(m-tolyl)-1', 2'-dihydro-3a'H-spiro[indene-2, 3'-pyrrolo[1, 2-a]quinoline]-1, 3-dione (4h): Yield 75%. Yellow solid, m.p. 158~160 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 7.89~7.87 (m, 1H, ArH), 7.85~7.83 (m, 1H, ArH), 7.76~7.72 (m, 4H, ArH), 7.27 (s, 1H, ArH), 7.26 (d, J＝3.2 Hz, 1H, ArH), 7.09 (d, J＝7.2 Hz, 1H, ArH), 7.01 (d, J＝7.6 Hz, 1H, ArH), 6.96 (t, J＝6.8 Hz, 2H, ArH), 6.89 (d, J＝7.2 Hz, 1H, ArH), 6.79 (d, J＝7.2 Hz, 1H, ArH), 6.58 (t, J＝7.6 Hz, 1H, ArH), 6.26 (d, J＝10.0 Hz, 1H, ArH), 6.00 (d, J＝8.0 Hz, 1H, CH), 5.75 (brs, 1H, CH), 5.72 (d, J＝9.6 Hz, 1H, CH), 4.96~4.95 (m, 1H, CH), 3.98 (d, J＝9.6 Hz, 1H, CH), 2.13 (s, 3H, CH₃); ¹³C NMR (100 MHz, CDCl₃) δ: 199.1, 197.2, 143.0, 142.7, 142.4, 140.0, 138.3, 135.9, 135.4, 133.5, 130.1, 129.3, 128.9, 128.8, 128.5, 127.6, 125.9, 123.0, 119.1, 118.0, 116.5, 109.7, 71.0, 70.2, 55.5, 21.1; IR (KBr) v: 2911, 1735, 1701, 1649, 1592, 1492, 1461, 1402, 1354, 1311, 1286, 1242, 1205, 1164, 1121, 1048, 1013, 979, 928, 858, 832, 753 cm^－1. HRMS (ESI) calcd for C₃₄H₂₄Cl- NNaO₃ [M+Na]⁺ 552.1337; found 552.1332.

1'-(4-Chlorobenzoyl)-2'-(3-chlorophenyl)-1', 2'-dihydro-3a'H-spiro[indene-2, 3'-pyrrolo[1, 2-a]quinoline]-1, 3-dione (4i): Yield 78%. Yellow solid, m.p.150~152 ℃; ¹H NMR (600 MHz, CDCl₃) δ: 7.91~7.89 (m, 1H, ArH), 7.87~7.85 (m, 1H, ArH), 7.79 (s, 1H, ArH), 7.78~7.77 (s, 1H, ArH), 7.31 (d, J＝8.4 Hz, 2H, ArH), 7.22 (s, 1H, ArH), 7.16 (d, J＝7.2Hz, 1H, ArH), 7.09~7.04 (m, 2H, ArH), 6.96 (t, J＝7.2Hz, 1H, ArH), 6.80 (d, J＝6.6 Hz, 1H, ArH), 6.61(t, J＝7.2 Hz, 1H, ArH), 6.27 (d, J＝10.2 Hz, 1H, ArH), 6.03 (d, J＝7.8 Hz, 1H, CH), 5.74~5.72 (m, 2H, CH), 4.97~4.95 (m, 1H, CH), 3.99 (d, J＝9.6 Hz, 1H, CH); ¹³C NMR (150 MHz, CDCl₃) δ: 198.9, 196.8, 143.0, 142.7, 142.4, 140.4, 136.2, 136.0, 135.7, 134.6, 133.4, 130.2, 130.0, 129.6, 129.3, 129.1, 128.6, 127.8, 127.3, 123.3, 119.2, 118.3, 116.3, 109.9, 71.0, 70.4, 70.2, 54.7; IR (KBr) v: 1734, 1700, 1647, 1593, 1492, 1461, 1403, 1383, 1353, 1310, 1286, 1242, 1204, 1164, 1121, 1092, 1047, 1005, 977, 928, 877, 854, 834, 781 cm^－1. HRMS (ESI) calcd for C₃₃H₂₁Cl₂NNaO₃ [M+Na]⁺ 572.0791; found 572.0791.

1'-(4-Chlorobenzoyl)-2'-(4-chlorophenyl)-1', 2'-dihydro-3a'H-spiro[indene-2, 3'-pyrrolo[1, 2-a]quinoline]-1, 3-dione(4j): Yield 70%. Yellow solid, m.p. 136~140 ℃; ¹H NMR (600 MHz, CDCl₃) δ: 7.90~7.88 (m, 1H, ArH), 7.85~7.83 (m, 1H, ArH), 7.80 (s, 1H, ArH), 7.78 (s, 1H, ArH), 7.77~7.76 (m, 2H, ArH), 7.32 (d, J＝8.4 Hz, 2H, ArH), 7.20 (d, J＝8.4 Hz, 2H, ArH), 7.09 (d, J＝8.4 Hz, 2H, ArH), 6.96 (t, J＝7.2 Hz, 1H, ArH), 6.80 (d, J＝7.2 Hz, 1H, ArH), 6.60 (t, J＝7.8 Hz, 1H, ArH), 6.27 (d, J＝10.2 Hz, 1H, ArH), 6.02 (d, J＝7.8 Hz, 1H, CH), 5.74 (s, 1H, CH), 5.71 (d, J＝9.6 Hz, 1H, CH), 4.97~4.95 (m, 1H, CH), 4.02 (d, J＝9.6 Hz, 1H, CH); ¹³C NMR (150 MHz, CDCl₃) δ: 199.0, 198.9, 196.9, 143.0, 142.7, 142.4, 140.4, 136.2, 135.8, 134.2, 133.4, 132.3, 130.5, 130.1, 129.5, 129.1, 129.0, 127.8, 123.2, 119.2, 118.3, 116.4, 109.9, 71.1, 70.3, 70.2, 54.6; IR (KBr) v: 2914, 2781, 1901, 1736, 1700, 1645, 1592, 1491, 1459, 1402, 1382, 1354, 1309, 1283, 1265, 1239, 1206, 1174, 1158, 1118, 1090, 1046, 1013, 977, 958, 924, 868, 834, 805, 780 cm^－1. HRMS (ESI) calcd for C₃₃H₂₁Cl₂NNaO₃ [M+Na]⁺ 572.0791; found 572.0784.

2'-(4-Bromophenyl)-1'-(4-chlorobenzoyl)-1', 2'-dihydro-3a'H-spiro[indene-2, 3'-pyrrolo[1, 2-a]quinoline]-1, 3-dione(4k): Yield 75%. Yellow solid, m.p. 142~144 ℃; ¹H NMR (600 MHz, CDCl₃) δ: 7.90~7.89 (m, 1H, ArH), 7.85~7.84 (m, 1H, ArH), 7.80 (s, 1H, ArH), 7.78~7.77 (m, 3H, ArH), 7.33 (t, J＝7.2 Hz, 2H, ArH), 7.24 (d, J＝9.0 Hz, 2H, ArH), 7.14 (d, J＝8.4 Hz, 2H, ArH), 6.95 (t, J＝7.8 Hz, 1H, ArH), 6.80 (d, J＝6.6 Hz, 1H, ArH), 6.60 (t, J＝7.2 Hz, 1H, ArH), 6.27 (d, J＝10.8 Hz, 1H, ArH), 6.03 (d, J＝8.4 Hz, 1H, CH), 5.74 (s, 1H, CH), 5.70 (d, J＝9.6 Hz, 1H, CH), 4.97~4.95 (m, 1H, CH), 4.01 (d, J＝9.6 Hz, 1H, CH); ¹³C NMR (150 MHz, CDCl₃) δ: 198.9, 196.9, 143.0, 142.7, 142.4, 140.4, 136.1, 135.7, 135.3, 133.5, 132.9, 132.1, 131.9, 130.8, 130.1, 130.0, 129.5, 129.1, 127.8, 123.2, 123.1, 122.4, 119.3, 118.3, 116.3, 109.9, 71.0, 70.3, 54.7; IR (KBr) v: 1736, 1700, 1645, 1592, 1491, 1460, 1402, 1402, 1382, 1354, 1310, 1283, 1265, 1240, 1207, 1159, 1119, 1090, 1074, 1047, 1010, 978, 959, 924, 868, 835, 805, 781 cm^－1. HRMS (ESI) calcd for C₃₃H₂₁BrClNNaO₃ [M+Na]⁺ 616.0286; found 616.0270.

1'-(4-Chlorobenzoyl)-2'-(3-nitrophenyl)-1', 2'-dihydro-3a'H-spiro[indene-2, 3'-pyrrolo[1, 2-a]quinoline]-1, 3-dione(4l): Yield 78%. Yellow solid, m.p. 138~140 ℃; ¹H NMR (600 MHz, CDCl₃) δ: 8.12 (s, 1H, ArH), 7.97 (d, J＝8.4 Hz, 1H, ArH), 7.91 (d, J＝4.8 Hz, 1H, ArH), 7.86~7.85 (m, 1H, ArH), 7.83 (d, J＝8.4 Hz, 1H, ArH), 7.79~7.77 (m, 2H, ArH), 7.65(d, J＝8.4 Hz, 1H, ArH), 7.34~7.32 (m, 3H, ArH), 7.00 (t, J＝7.2 Hz, 1H, ArH), 6.82 (d, J＝7.2 Hz, 1H, ArH), 6.64 (d, J＝7.2 Hz, 1H, ArH), 6.29 (d, J＝10.2 Hz, 1H, ArH), 6.10 (d, J＝7.8 Hz, 1H, CH), 5.80 (d, J＝9.6 Hz, 1H, CH), 5.76 (s, 1H, CH), 4.97~4.95 (m, 1H, CH), 4.16 (d, J＝9.6 Hz, 1H, CH); ¹³C NMR (150 MHz, CDCl₃) δ: 198.8, 198.6, 196.4, 143.3, 142.9, 142.6, 142.3, 140.5, 136.3, 136.2, 135.9, 135.1, 133.4, 130.3, 130.0, 129.8, 129.7, 129.2, 127.9, 124.1, 123.3, 119.3, 118.6, 116.1, 110.1, 71.0, 70.5, 54.2; IR (KBr) v:1733, 1700, 1643, 1589, 1534, 1492, 1460, 1403, 1381, 1351, 1307, 1287, 1265, 1242, 1203, 1179, 1161, 1118, 1094, 1047, 1015, 975, 926, 881, 858, 831, 812, 780, 759 cm^－1. HRMS (ESI) calcd for C₃₃H₂₁ClN₂NaO₅ [M+Na]⁺ 583.1031; found 583.1015.

Ethyl 1, 3-dioxo-2'-phenyl-1, 1', 2', 3-tetrahydro-3a'H-spiro[indene-2, 3'-pyrrolo[1, 2-a]-quinoline]-1'-carboxylate (5a): Yield 75%. Yellow solid, m.p. 194~196 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 7.97~7.90 (m, 3H, ArH), 7.80~7.79 (m, 1H, ArH), 7.20~7.17 (m, 5H, ArH), 7.09 (t, J＝8.0 Hz, 1H, ArH), 6.84 (d, J＝7.6 Hz, 1H, ArH), 6.61 (t, J＝7.2 Hz, 1H, ArH), 6.32~6.31 (m, 1H, ArH), 6.29 (brs, 1H, CH), 5.46 (s, 1H, CH), 5.10 (d, J＝9.6 Hz, 1H, CH), 4.90 (d, J＝9.6 Hz, 1H, CH), 4.18~4.12 (m, 3H, CH), 1.09 (t, J＝7.6 Hz, 3H, CH₃); ¹³C NMR (100 MHz, CDCl₃) δ: 199.0, 197.5, 173.1, 143.6, 142.7, 142.5, 135.9, 135.4, 133.8, 130.2, 129.3, 128.6, 128.5, 127.9, 127.5, 123.1, 123.0, 119.0, 118.1, 116.3, 110.0, 70.8, 69.8, 67.7, 61.5, 54.3, 14.1; IR (KBr) v: 3021, 2982, 2902, 1741, 1698, 1645, 1594, 1493, 1398, 1354, 1237, 1182, 1010, 965, 860, 753 cm^－1. HRMS (ESI) calcd for C₂₉H₂₄NO₄ [M+H]⁺ 450.1700; found 450.1705.

Ethyl 1, 3-dioxo-2'-(m-tolyl)-1, 1', 2', 3-tetrahydro-3a'H- spiro[indene-2, 3'-pyrrolo[1, 2-a]-quinoline]-1'-carboxylate (5b): Yield 71%. Yellow solid, m.p. 154~156 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 7.91~7.90 (m, 1H, ArH), 7.77~7.72 (m, 3H, ArH), 7.09~7.01 (m, 4H, ArH), 6.91~6.89 (m, 1H, ArH), 6.77~6.76 (m, 1H, ArH), 6.63~6.62 (m, 1H, ArH), 6.42~6.41 (m, 1H, ArH), 6.21 (d, J＝7.2 Hz, 1H, CH), 5.63 (s, 1H, CH), 4.99-4.92 (m, 2H, CH), 4.23~4.21 (m, 3H, CH), 2.18 (s, 3H, CH₃), 1.24~1.14 (m, 3H, CH₃); ¹³C NMR (100 MHz, CDCl₃) δ: 198.9, 197.6, 173.1, 143.6, 142.8, 142.6, 138.0, 135.8, 135.3, 133.7, 130.1, 129.4, 129.3, 128.7, 128.3, 127.5, 125.6, 123.0, 122.9, 119.0, 118.0, 116.3, 110.0, 70.8, 69.8, 67.7, 61.4, 54.3, 21.3, 14.1; IR (KBr) v: 3026, 2975, 2825, 1732, 1702, 1648, 1594, 1491, 1363, 1298, 1172, 1020, 926, 876, 836, 779, 745, 701 cm^－1. HRMS (ESI) calcd for C₃₀H₂₆NO₄ [M+H]⁺ 464.1856; found 464.1866.

Ethyl 1, 3-dioxo-2'-(p-tolyl)-1, 1', 2', 3-tetrahydro-3a'H- spiro[indene-2, 3'-pyrrolo[1, 2-a]quinoline]-1'-carboxylate(5c): Yield 58%. Yellow solid, m.p. 143~145 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 7.89~7.88 (m, 1H, ArH), 7.77~7.70 (m, 3H, ArH), 7.13~7.07 (m, 4H, ArH), 6.92~6.90 (m, 2H, ArH), 6.76~6.74 (m, 1H, ArH), 6.61~6.59 (m, 1H, ArH), 6.40~6.38 (m, 1H, ArH), 6.20~6.18 (m, 1H, CH), 5.62 (s, 1H, CH), 4.96~4.89 (m, 2H, CH), 4.23~4.19 (m, 3H, CH), 2.16 (s, 3H, CH₃), 1.20~1.16 (m, 3H, CH₃); ¹³C NMR (100 MHz, CDCl₃) δ: 199.1, 197.6, 173.1, 143.7, 142.9, 142.6, 137.6, 136.0, 135.8, 135.3, 130.7, 130.2, 129.3, 129.2, 128.5, 127.5, 125.7, 123.1, 123.0, 119.1, 118.1, 116.4, 110.0, 70.9, 69.9, 67.8, 61.5, 54.1, 20.9, 14.2; IR (KBr) v: 3021, 2984, 2885, 1738, 1705, 1652, 1595, 1496, 1460, 1368, 1184, 1017, 958, 750 cm^－1. HRMS (ESI) calcd for C₃₀H₂₆NO₄ [M+ H]⁺ 464.1856; found 464.1877.

Ethyl 2'-(3-methoxyphenyl)-1, 3-dioxo-1, 1', 2', 3-tetrahy- dro-3a'H-spiro[indene-2, 3'-pyrrolo[1, 2-a]quinoline]-1'-carboxylate (5d): Yield 64%. Yellow solid, m.p. 130~132 ℃; ¹H NMR (600 MHz, CDCl₃) δ: 7.91~7.90 (m, 1H, ArH), 7.78~7.73 (m, 3H, ArH), 7.09~7.04 (m, 2H, ArH), 6.84~6.76 (m, 3H, ArH), 6.65~6.63 (m, 2H, ArH), 6.40 (d, J＝6.0 Hz, 1H, ArH), 6.21 (d, J＝9.0 Hz, 1H, CH), 5.63 (s, 1H, CH), 4.98~4.92 (m, 2H, CH), 4.23 (brs, 3H, CH), 3.67 (s, 3H, OCH₃), 1.21~1.20 (m, 3H, CH₃); ¹³C NMR (150 MHz, CDCl₃) δ: 199.0, 197.5, 173.1, 159.5, 143.6, 142.9, 142.6, 135.9, 135.4, 130.2, 129.5, 129.4, 127.5, 123.1, 123.0, 121.0, 119.1, 118.1, 116.3, 114.1, 113.8, 110.0, 70.7, 69.8, 67.8, 61.5, 55.1, 54.4, 14.2; IR (KBr) v: 3033, 2975, 1706, 1598, 1462, 1364, 1235, 1178, 1100, 1019, 864, 793, 754 cm^－1. HRMS (ESI) calcd for C₃₀H₂₆NO₅ [M+H]⁺ 480.1805; found 480.1822.

Ethyl 2'-(3-chlorophenyl)-1, 3-dioxo-1, 1', 2', 3-tetrahydro- 3a'H-spiro[indene-2, 3'-pyrrolo[1, 2-a]quinoline]-1'-carboxy- late (5e): Yield 65%. Yellow solid, m.p. 154~156 ℃; ¹H NMR (400 MHz, DMSO-d₆) δ: 8.05~7.98 (m, 2H, ArH), 7.95 (brs, 1H, ArH), 7.86~7.84 (m, 1H, ArH), 7.26~7.20 (m, 3H, ArH), 7.15~7.13 (m, 1H, ArH), 7.09(t, J＝7.2Hz, 1H, ArH), 6.85 (d, J＝6.4 Hz, 1H, ArH), 6.62 (t, J＝7.2 Hz, 1H, ArH), 6.34~6.30 (m, 1H, ArH), 5.43 (s, 1H, CH), 5.11~5.08 (m, 1H, CH), 4.90 (d, J＝9.2 Hz, 1H, CH), 4.19~4.15 (m, 2H, CH₂), 1.10 (t, J＝7.2 Hz, 3H, CH₃); ¹³C NMR (150 MHz, CDCl₃) δ: 200.0, 198.9, 197.0, 143.1, 142.4, 136.2, 136.0, 135.6, 135.3, 134.4, 133.6, 133.2, 132.7, 130.6, 130.2, 129.8, 129.5, 128.7, 128.6, 128.4, 127.7, 127.3, 123.2, 119.2, 118.1, 116.3, 109.9, 71.1, 70.5, 70.1, 54.9; IR (KBr) v: 1734, 1700, 1647, 1594, 1529, 1492, 1460, 1446, 1406, 1381, 1354, 1311, 1286, 1241, 1205, 1180, 1162, 1120, 1081, 1047, 1001, 976, 926, 895, 876, 850, 812, 775 cm^－1. HRMS (ESI) calcd for C₃₃H₂₂Cl- NNaO₃ [M+Na]⁺ 538.1200; found 538.1179.

2'-(3-Chlorophenyl)-1'-(4-nitrophenyl)-1', 2'-dihydro-3a'H-spiro[indene-2, 3'-pyrrolo[1, 2-a]quinoline]-1, 3-dione(5f): Yield 79%. Yellow solid, m.p. 128~130 ℃; ¹H NMR (600 MHz, CDCl₃) δ: 8.16 (d, J＝9.0 Hz, 2H, ArH), 7.91~7.89 (m, 1H, ArH), 7.87~7.86 (m, 1H, ArH), 7.79~7.76 (m, 2H, ArH), 7.37 (d, J＝8.4 Hz, 2H, ArH), 7.24 (s, 1H, ArH), 7.18 (d, J＝7.8 Hz, 1H, ArH), 7.15~7.10 (m, 2H, ArH), 6.95~6.93 (m, 1H, ArH), 6.82 (d, J＝6.6Hz, 1H, ArH), 6.63 (t, J＝7.2 Hz, 1H, ArH), 6.31 (d, J＝10.2 Hz, 1H, ArH), 6.04 (d, J＝7.8 Hz, 1H, CH), 5.72 (brs, 1H, CH), 5.56 (d, J＝10.2 Hz, 1H, CH), 5.03~5.00 (m, 1H, CH), 3.82 (d, J＝10.2 Hz, 1H, CH); ¹³C NMR (150 MHz, CDCl₃) δ: 199.6, 197.0, 149.7, 143.8, 142.8, 142.5, 136.1, 135.8, 135.6, 134.7, 130.1, 129.6, 128.7, 127.7, 127.4, 126.2, 124.5, 123.2, 119.1, 118.5, 116.1, 110.6, 71.4, 70.4, 70.5, 59.2; IR (KBr) v: 1734, 1701, 1649, 1595, 1572, 1518, 1492, 1456, 1436, 1400, 1376, 1343, 1306, 1261, 1237, 1179, 1163, 1109, 1086, 1047, 997, 964, 923, 895, 877, 840, 805, 783 cm^－1. HRMS (ESI) calcd for C₃₂H₂₁ClN₂NaO₄ [M+Na]⁺ 555.1082; found 555.1072.

1'-(4-Nitrophenyl)-2'-(m-tolyl)-1', 2'-dihydro-3a'H-spiro-[indene-2, 3'-pyrrolo[1, 2-a]quinoline]-1, 3-dione (5g): Yield 75%. Yellow solid, m.p. 166~168 ℃; ¹H NMR (600 MHz, CDCl₃) δ: 8.14 (d, J＝8.4 Hz, 2H, ArH), 7.86 (d, J＝24.0 Hz, 2H, ArH), 7.74 (s, 2H, ArH), 7.37 (d, J＝7.8 Hz, 2H, ArH), 7.08~7.04 (m, 2H, ArH), 6.99 (s, 1H, ArH), 6.95~6.92 (m, 2H, ArH), 6.81 (d, J＝6.0 Hz, 1H, ArH), 6.62(t, J＝7.2 Hz, 1H, ArH), 6.30 (d, J＝10.2 Hz, 1H, ArH), 6.04 (d, J＝6.6 Hz, 1H, CH), 5.73 (s, 1H, CH), 5.58 (d, J＝9.6 Hz, 1H, CH), 5.04 (d, J＝9.0 Hz, 1H, CH), 3.80 (d, J＝9.6 Hz, 1H, CH), 2.19 (s, 3H, CH₃); ¹³C NMR (100 MHz, CDCl₃) δ: 199.4, 197.6, 150.1, 147.4, 143.9, 142.8, 142.5, 138.4, 135.9, 135.4, 133.3, 130.0, 129.4, 128.6, 127.5, 126.2, 126.1, 124.3, 123.1, 123.0, 119.1, 118.3, 116.3, 110.5, 71.4, 71.3, 69.8, 59.7, 21.3; IR (KBr) v: 2917, 1792, 1734, 1702, 1652, 1597, 1519, 1492, 1457, 1400, 1342, 1307, 1238, 1180, 1110, 1048, 1011, 965, 927, 879, 850, 785 cm^－1. HRMS (ESI) calcd for C₃₃H₂₄N₂NaO₄ [M+ Na]⁺ 535.1628; found 535.1612.

Supporting Information ¹H NMR and ¹³C NMR spectra of all compounds. Single-crystal X-ray data for compounds 1a (CCDC 1956691), 1f (CCDC 1956692), 2a (CCDC 1956693), 3a (CCDC 1956694), 3g (CCDC 1956695), 3k (CCDC 1956696), 3l (CCDC 1956697), 4d (CCDC 1859568), 4e (CCDC 1859569) and 5a (CCDC 1859570) have been deposited at the Cambridge Crystallographic Database Center (http//www.ccdc.cam.ac.uk). The Supporting Information is available free of charge via the Internet at http://sioc-journal.cn/.

1. [1]
  (a) Addla, D.; Bhima; Sridhar, B.; Devi, A.; Kantevari, S. Bioorg. Med. Chem. Lett. 2012, 22, 7475.
  (b) Chakrabarty, S.; Croft, M. S.; Marko, M. G.; Moyna, G. Bioorg. Med. Chem. 2013, 21, 1143/
  (c) Muscia, G. C.; Buldain, G. Y.; Asis, S. E. Eur. J. Med. Chem. 2014, 73, 243.
2. [2]
  (a) Huang, H.-H.; Prabhakar, Ch.; Tang, K.-C.; Chou, P. T.; Huang, G. J.; Yang, J. S. J. Am. Chem. Soc. 2011, 133, 8028.
  (b) Gomez-Esteban, S.; Benito-Hernandez, A.; Termine, R.; Hennrich, G.; Navarrete, J. T. L.; Ruiz Delgado, M. C.; Golemme, A.; Gomez-Lor, B. Chem.-Eur. J. 2018, 24, 3576.
  (c) Sanguinet, L.; Williams, J. C.; Yang, Z. Y.; Twieg, R. J.; Mao, G. L.; Singer, K. D.; Wiggers, G.; Petschek, R. G. Chem. Mater. 2006, 18, 425.
3. [3]
  (a) Mondal, A.; Mukhopadhyay, C. ACS Comb. Sci. 2015, 17, 404.
  (b) Mondal, A.; Banerjee, B.; Bhaumik, A.; Mukhopadhyay, C. ChemCatChem 2016, 8, 1185.
  (c) Xu, H.; Chen, K.; Liu, H. W.; Wang, G. W. Org. Chem. Front. 2018, 5, 2864.
  (d) Hussein, E. M.; Moussa, Z.; Ahmed, S. A. Monatsh. Chem. 2018, 149, 2021.
4. [4]
  (a) Zhou, Y. J.; Chen, D. S.; Li, Y. L.; Liu, Y.; Wang, X. S. ACS Comb. Sci. 2013, 15, 498.
  (b) Chen, M.; Sun, N.; Liu, Y. H. Org. Lett. 2013, 15, 5574.
  (c) Allais, C.; Lieby-Muller, F.; Rodriguez, J.; Constantieux, T. Eur. J. Org. Chem. 2013, 4131.
  (d) Marquise, N.; Dorcet, V.; Chevallier, F.; Mongin, F. Org. Biomol. Chem. 2014, 12, 8138.
5. [5]
  (a) Mei, G. J.; Shi, F.; Chem. Commun. 2018, 54, 6607.
  (b) Mei, G. J.; Li, D.; Zhou, G. X.; Shi, F.; Cao, Z. Chem. Commun. 2017, 53, 10030.
  (c) Wu, J. L.; Du, B. X.; Zhang, Y. C.; He, Y. Y.; Wang, J. Y.; Wu, P.; Shi, F. Adv. Synth. Catal. 2016, 358, 2777.
  (d) Zhu, Q. N.; Zhang, Y. C.; Xu, M. M.; Sun, X. X.; Yang, X.; Shi, F. J. Org. Chem. 2016, 81, 7898.
  (e) Zhao, K.; Zhi, Y.; Shu, T.; Valkonen, A.; Rissanen, K.; Enders, D. Angew. Chem., Int. Ed. 2016, 55, 12104.
  (f) Abbaraju, S.; Ramireddy, N.; Rana, N. K.; Arman, H. J.; Zhao, C. G. Adv. Synth. Catal. 2015, 357, 2633.
6. [6]
  (a) Abdukader, A.; Zhang, Y. H.; Zhang, Z. P.; Liu, C. J. Chin. J. Org. Chem. 2016, 36, 875 (in Chinese).
  (阿布力米提·阿布都卡德尔, 张永红, 张增鹏, 刘晨江, 有机化学, 2016, 36, 875.)
  (b) Tian, W. Y.; Xu, S.; Liang, Z. W.; Sun, D. L.; Zhang, R. H. Chin. J. Org. Chem. 2016, 36, 2121 (in Chinese).
  (田文艳, 徐松, 梁中卫, 孙德立, 张荣华, 有机化学, 2016, 36, 2121.)
  (c) Hao, E. J.; Jiang, X. H.; Fu, D. D.; Wang, D. C.; Xie, M. S.; Qu, G. R.; Guo, H. M. Chin. J. Org. Chem. 2016, 36, 2746 (in Chinese).
  (郝二军, 蒋小涵, 付丹丹, 王东超, 谢明胜, 渠桂荣, 郭海明, 有机化学, 2016, 36, 2746.)
  (d) Tian, K.; Meng, J.; Gan, Y. Y.; Li, X. Q.; Wu, S. Q.; Chen, J.; Li, W.; Qi, Y. Y.; Hu, W. N.; Wang, Z. C.; Ouyang G. P. Chin. J. Org. Chem. 2018, 38, 2657 (in Chinese).
  (田坤, 孟娇, 甘宜远, 李小琴, 巫受群, 陈洁, 李文, 漆亚云, 胡伟男, 王贞超, 欧阳贵平, 有机化学, 2018, 38, 2657.)
7. [7]
  (a) Tugrak, M.; Inci Gul, H.; Sakagami, H.; Gulcin, I.; Supuran, C. T. Bioorg. Chem. 2018, 81, 433.
  (b) Jangra, H.; Chen, Q.; Fuks, E.; Zenz, I.; Mayer, P.; Ofial, A. R.; Zipse, H.; Mayr, H. J. Am. Chem. Soc. 2018, 140, 16758.
  (c) Chen, Y. R.; Ganapuram, M. R.; Hsieh, K. H.; Chen, K. H.; Karanam, P.; Vagh, S. S.; Liou, Y. C.; Lin, W. W. Chem. Commun. 2018, 54, 12702.
  (d) Xu, H.; Sha, F.; Li, Q.; Wu, X. Y. Org. Biomol. Chem. 2018, 16, 7214.
8. [8]
  (a) Wang, X. H.; Yan, C.-G. Synthesis 2014, 46, 1059.
  (b) Shi, Y. G.; Wang, X. H.; Liu, R. Z.; C. G. Yan, Chem. Commun. 2016, 52, 6280.
  (c) Zhang, Y. Y.; Han, Y.; Sun, J.; Yan, C. G. ChemistrySelect 2017, 2, 7382.
  (d) Cao, J.; Sun, J. Yan, C. G. Org. Biomol. Chem. 2018, 16, 4170.
  (e) Sun, J.; Zhang, Y.; Shi, R. G.; Yan, C. G. Org. Biomol. Chem. 2019, 17, 3978.
  (f) Liu, D.; Sun, J.; Zhang, Y.; Yan, C. G. Org. Biomol. Chem. 2019, 17, 8008.
  (g) Yang, W. J.; Fang, H. L.; Sun, J. Yan, C. G. ACS Omega 2019, 4, 13553.
  (h) Huang, Y.; Fang, H. L.; Huang, Y. X.; Sun, J.; Yan, C. G. J. Org. Chem. 2019, 84, 1912437.
9. [9]
  (a) Kröhnke, F.; Zecher, W. Angew. Chem., Int. Ed. 1962, 1, 626.
  (b) Kröhnke, F. Angew. Chem., Int. Ed. 1963, 2, 225.
  (c) Jacobs, J.; Van Hende, E.; Claessens, S.; De Kimpe, N. Curr. Org. Chem. 2011, 15, 1340.
  (d) Bull, J. A.; Mousseau, J. J.; Pelletier, G.; Charette, A. B. Chem. Rev. 2012, 112, 2642.
10. [10]
  (a) Constable, E. C.; Edwards, A. J.; Martínez-Máńez, R.; Raithby, P. R. J. Chem. Soc., Dalton Trans. 1995, 3253.
  (b) Eryazici, I.; Moorefield, C. N.; Durmus, S.; Newkone, G. R. J. Org. Chem. 2006, 71, 1009.
  (c) Tu, S. J.; Jia, R. H.; Jiang, B.; Zhang, J. Y.; Zhang, Y.; Yao, C. S.; Ji, S. J. Tetrahedron 2007, 63, 381.
11. [11]
  (a) Bora, U.; Saikia, A.; Boruah, R. C. Org. Lett. 2003, 5, 435.
  (b) Sasaki, T.; Kanematsu, K.; Yukimoto, Y.; Ochiai, S. J. Org. Chem. 1971, 36, 813.
  (c) Xia, Z. Q.; Przewloka, T.; Koya, K.; Ono, M.; Chen, S. J.; Sun, L. J. Tetrahedron Lett. 2006, 47, 8817.
12. [12]
  (a) Dinica, R. M.; Druta, I. I.; Pettinari, C. Synlett 2000, 1013.
  (b) Furdui, B.; Dinica, R.; Druta, I. I.; Demeunynck, M. Synthesis 2006, 2640.
13. [13]
  (a) Zhang, X. C.; Huang, W. Y. Synthesis 1999, 1, 51.
  (b) Wu, K.; Chen, Q. Y. Synthesis 2003, 35.
  (c) Chuang, C. P.; Tsai, A. I. Synthesis 2006, 675.
14. [14]
  (a) Ruano, J. L. G.; Fraile, A.; Martín, M. R.; González, G.; Fajardo, C.; Martín-Castro, A. M. J. Org. Chem. 2011, 76, 3296.
  (b) Khlebnikov, A. F.; Golovkina, M. V.; Novikov, M. S.; Yufit, D. S. Org. Lett. 2012, 14, 3768.
  (c) Brioche, J.; Meyer, C.; Cossy, J. Org. Lett. 2015, 17, 2800.
15. [15]
  (a) Liu, Y.; Sun, J. W. J. Org. Chem. 2012, 77, 1191.
  (b) Osyanin, V. A.; Osipov, D. V.; Klimochkin, Y. N. J. Org. Chem. 2013, 78, 5505.
  (c) Wang, F. Y.; Shen, Y. M.; Hu, H. Y.; Wang, X. S.; Wu, H.; Liu, Y. J. Org. Chem. 2014, 79, 9556.
16. [16]
  (a) Allgäuer, D. S.; Mayer, P.; Mayr, H. J. Am. Chem. Soc. 2013, 135, 15216.
  (b) Allgäuer, D. S.; Mayr, H. Eur. J. Org. Chem. 2013, 6379.
  (c) Allgäuer, D. S.; Mayr, H. Eur. J. Org. Chem. 2014, 2956.
  (d) Hopf, H.; Jones, P. G.; Nicolescu, A.; Bicu, E.; Birsa, L. M.; Belei, D. Chem.-Eur. J. 2014, 20, 5565.
17. [17]
  (a) Yan, C. G.; Cai, X. M.; Wang, Q. F.; Wang, T. Y.; Zheng, M. Org. Biomol. Chem. 2007, 5, 945.
  (b) Yan, C. G.; Song, X. K.; Wang, Q. F.; Sun, J. Siemeling, U.; Bruhn, C. Chem. Commun. 2008, 1440.
  (c) Wang, Q. F.; Song, X. K.; Chen, J.; Yan, C. G. J. Comb. Chem. 2009, 11, 1007.
  (d) Wang, Q. F.; Hou, H.; Hui, L.; Yan, C. G. J. Org. Chem. 2009, 74, 7403.
  (e) Yan, C. G.; Wang, Q. F.; Song, X. K.; Sun, J. J. Org. Chem. 2009, 74, 710.
  (f) Wang, Q. F.; Hui, L.; Hou, H.; Yan, C. G. J. Comb. Chem. 2010, 12, 260.
  (g) Han, Y.; Chen, J.; Hui, L.; Yan, C. G. Tetrahedron 2010, 66, 7743.
18. [18]
  (a) Hou, H.; Zhang, Y.; Yan, C. G. Chem. Commun. 2012, 48, 4492.
  (b) Hui, L.; Li, H. Y.; Yan, C. G. Eur. J. Org. Chem. 2012, 3157.
  (c) Wu, L.; Sun, J.; Yan. C. G. Org. Biomol. Chem. 2012, 10, 9452.
  (d) Shen, G. L.; Sun, J.; Yan, C. G. Org. Biomol. Chem., 2015, 13, 10929.
  (e) Shen, G. L.; Sun, J.; Yan, C. G. RSC Adv. 2015, 5, 4475.
  (f) Liu, L. Z.; Wang, X. Y.; Sun, J.; Yan, C. G. Tetrahedron Lett. 2015, 56, 6711.
19. [19]
  (a) Banothu, J.; Basavoju, S.; Bavantula, R. J. Heterocycl. Chem. 2015, 52, 853.
  (b) Majumder, S.; Sharma, M.; Bhuyan, P. J. Tetrahedron Lett. 2013, 54, 6868.
20. [20]
  (a) Shen, G. L.; Sun, J.; Yan, C. G. Chin. J. Chem. 2016, 34, 412.
  (b) Liu, R. Z.; Shi, R. G.; Sun, J.; Yan, C. G. Org. Chem. Front. 2017, 4, 354.
  (c) Shi, R. G.; Sun, J.; Yan, C. G. ACS Omega 2017, 2, 7820.
21. [21]
  (a) Fujita, R.; Hoshino, M.; Tojyo, Y.; Kimura, A.; Hongo, H. Yakugaku Zasshi 2006, 126, 99.
  (b) Fujita, R.; Watanabe, N.; Tomisawa, H. Heterocycles 2001, 55, 435.
  (c) Fujita, R.; Hoshino, M.; Tomisawa, H. Chem. Pharm. Bull. 2006, 54, 334.

Figure 1 Single crystal structure of compound 1a

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Figure 2 Single crystal structure of compound 2a

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Figure 3 Single crystal structure of compound 3a

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Figure 4 Single crystal structure of the compound 3l

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Scheme 1 Plausible reaction mechanism

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Figure 5 Single crystal structure of compound 4d

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Figure 6 Single crystal structure of the compound 5a

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Table 1. Reaction of quinolinium salts with 1, 3-indanedione^a


Entry	R	1	Yield^b/% of 1	2	Yield^b/% of 2
1	C₆H₅	1a	59	2a	12
2	p-CH₃C₆H₄	1b	61	2b	13
3	p-ClC₆H₄	1c	65	2c
4	p-BrC₆H₄	1d	58	2d	14
5	OMe	1e	57	2e
6	OEt	1f	63	2f	10
^a Reaction conditions: quinolinium salt (1.2 mmol), 1, 3-indanedione (0.5 mmol), Et₃N (1.5 mmol), EtOH (15.0 mL), r.t., 4 h; ^b Isolated yields.

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Table 2. Reactions of N-benzylquinolinium salts with 1, 3-in- danedione^a


Entry	Compd.	R	Ar	Yield/%
1	3a	H	C₆H₅	68
2	3b	H	p-CH₃OC₆H₄	72
3	3c	H	p-CH₃C₆H₄	71
4	3d	H	p-t-BuC₆H₄	77
5	3e	H	3, 5-(CH₃O)₂C₆H₃	76
6	3f	H	p-ClC₆H₄	75
7	3g	H	m-ClC₆H₄	78
8	3h	H	p-BrC₆H₄	73
9	3i	H	p-CF₃C₆H₄	75
10	3j	H	p-NO₂C₆H₄	77
11	3k	H	n-Pr	70
12	3l	CH₃	C₆H₅	72
13	3m	CH₃	p-FC₆H₄	72
14	3n	CH₃	p-ClC₆H₄	78
15	3o	CH₃	p-BrC₆H₄	77
^a Reaction conditions: quinolinium salt (0.5 mmol), 1, 3-indanedione (0.5 mmol), Et₃N (1.0 mmol), EtOH (15.0 mL), r.t., 4 h; ^b Isolated yields.

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Table 3. Synthesis of spiro[indene-2, 3'-pyrrolo[1, 2-a]quino-line]s 4a~4l^a


Entry	Compd.	Ar	Ar	Yield^b/%
1	4a	C₆H₅	p-CH₃C₆H₄	76
2	4b	C₆H₅	m-ClC₆H₄	76
3	4c	C₆H₅	p-BrC₆H₄	78
4	4d	C₆H₅	m-NO₂C₆H₄	74
5	4e	p-CH₃OC₆H₄	m-CH₃OC₆H₄	90
6	4f	p-ClC₆H₄	C₆H₅	71
7	4g	p-ClC₆H₄	p-CH₃C₆H₄	75
8	4h	p-ClC₆H₄	m-CH₃C₆H₄	75
9	4i	p-ClC₆H₄	m-ClC₆H₄	78
10	4j	p-ClC₆H₄	p-ClC₆H₄	70
11	4k	p-ClC₆H₄	p-BrC₆H₄	75
12	4l	p-ClC₆H₄	m-O₂NC₆H₄	78
^a Reaction conditions: quinolinium salt (0.6 mmol), aromatic aldehyde (0.5 mmol), 1, 3-indanedione (0.5 mmol), Et₃N (0.5 mmol), EtOH (10.0 mL); r.t., 5 h. ^b Isolated yield.

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Table 4. Synthesis of spiro[indene-2, 3'-pyrrolo[1, 2-a]quinoli-ne]s 5a~5g^a


Compd.	EWG	Ar	Yield^b/%
5a	CO₂C₂H₅	C₆H₅	65
5b	CO₂C₂H₅	m-CH₃C₆H₄	71
5c	CO₂C₂H₅	p-CH₃C₆H₄	58
5d	CO₂C₂H₅	m-CH₃OC₆H₄	64
5e	CO₂C₂H₅	m-ClC₆H₄	65
5f	p-O₂NC₆H₄	m-ClC₆H₄	79
5g	p-O₂NC₆H₄	m-CH₃C₆H₄	75
^a Reaction conditions: quinolinium salt (0.6 mmol), aromatic aldehyde (0.5 mmol), 1, 3-indanedione (0.5 mmol), Et₃N (0.5 mmol), EtOH (10.0 mL); r.t., 5 h. ^b Isolated yield.

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沈阳化工大学材料科学与工程学院沈阳 110142