Catalyst-Free, Visible-Light Promoted One-Pot Synthesis of

Research Article pubs.acs.org/journal/ascecg

Catalyst-Free, Visible-Light Promoted One-Pot Synthesis of Spirooxindole-Pyran Derivatives in Aqueous Ethyl Lactate Mo Zhang, Qiu-Yang Fu, Ge Gao, He-Ye He, Ying Zhang, Yin-Su Wu,* and Zhan-Hui Zhang* College of Chemistry and Material Science, Hebei Normal University, No. 20 Road East. 2nd Ring South, Shijiazhuang 050024, People’s Republic of China S Supporting Information *

ABSTRACT: A highly efficient, eco-friendly protocol has been developed for synthesis of spirooxindole-pyran derivatives via one-pot, three-component reaction of isatins, malononitrile, and enolizable C−H activated compounds (2-hydroxynaphthalene1,4-dione, 4-hydroxycoumarine and dimedone) under visible-light irradiation in water-ethyl lactate at room temperature. The reported approach shows significant advantages such as a high yield, mild and clean reaction conditions, the application of clean visible light as a source of energy, the absence of catalyst, the use of ethyl lactate/water as an environmentally friendly solvent, a one-pot multicomponent reaction at room temperature, no chromatographic separation, and applicability for large-scale synthesis. KEYWORDS: Visible-light, Catalyst-free, Spirooxindoles, Multicomponent reaction, Heterocyclic compounds, Ethyl lactate

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of terminal alkynes,19 the thioacetalization of aldehydes,20 the reaction of furfural and amines,21 and the synthesis of 1,4dihydropyridines22 and 4(3H)-quinazolinones.23 In addition, catalyst-free synthetic methods not only attract attention to laboratory synthesis but also draw attention in the chemical industry because of a lower cost, reduced pollution, and ease of purification.24,25 With these aspects of green synthesis in mind, the development of catalyst-free, visible light-promoted multicomponent reactions in environmentally benign media would be of considerable interest. Polyheterocyclic compounds have particularly emerged as attractive and valuable synthetic targets because they show structural complexity, versatility, and diversity. The importance of this type of complex molecular framework in the pharmaceutical industry, agriculture, materials science, and coordination chemistry has been demonstrated.26 Spirooxindole represents essential substructures and possesses interesting structural properties and strong bioactivity profiles, such as antimicrobial,27 potent MR antagonist,28 anticancer,29 antibacterial, antifungal, antimalarial, and antitubercular activities.30 The pyran motif is also one of the commonly used chemical scaffolds, which constitute the key core of various natural

INTRODUCTION Over the past decade, the development of a high efficiency, high selectivity, green, safe, atom- and step-economical synthesis strategy has become of paramount importance in the field of organic chemistry. One of the most promising environmental approaches is the use of light in combination with a green solvent to develop one-pot multicomponent reactions (MCRs).1,2 Visible light has been used as a source of energy in the field of organic synthesis in recent years because of its low cost, abundant reserves and clean, nontoxic, nonpolluting, abundant, and renewable characteristics.3−5 One-pot MCR is a powerful tool in organic, combinatorial, and medicinal chemistry because it can shorten the reaction time, simplify the separation step, reduce costs, and give a relatively higher total chemical yield compared to multistep synthesis.6 Replacement of harmful organic solvents with an eco-friendly medium is one of the major focal points of green chemistry.7−13 In recent years, ethyl lactate has been introduced as a new alternative sustainable solvent for organic synthesis with intrinsic advantages of nontoxicity, a low cost, nontoxic full degradability, good stability, and solubility in both water and organic compounds.14 It has been applied to the Suzuki− Miyaura cross-coupling reaction,15 cross-coupling reactions of enaminones and thiophenols,16 the 1,3-dipolar cycloaddition reaction,17 the CC bond cleavage of 1,3-diketones and enaminones,18 Glaser-type homo- and cross-coupling reactions © 2017 American Chemical Society

Received: April 11, 2017 Revised: May 15, 2017 Published: May 20, 2017 6175

DOI: 10.1021/acssuschemeng.7b01102 ACS Sustainable Chem. Eng. 2017, 5, 6175−6182

Research Article

ACS Sustainable Chemistry & Engineering products as well as photochromic materials.31 Amino-4Hpyrans are employed as laser dyes, optical brighteners, pigments, cosmetics, fluorescence markers, and potent biodegradable agrochemicals.32 Due to the important aforementioned properties of spirooxindole-pyran derivatives, a variety of synthetic strategies have been developed for preparation of this bicyclic compound. The most straightforward synthesis of this heterocyclic system involves a multicomponent coupling of an isatins with malononitrile and diverse enolizable C−H activated acidic compounds.33 However, these reported methods are associated with some drawbacks, such as the use of costly catalysts, a low yield of the product, a high temperature, and difficulty in the recovery of high boiling solvent. Thus, there was a need to design an expedient, mild, general, and eco-friendly protocol for the construction of spirooxindole-pyran derivatives. On the basis of the above analysis and continuing our research program about the development of environmentally friendly approaches for the construction of heterocyclic molecules,34−39 we report herein a highly efficient route to constructing spirooxindole pyran derivatives via visible-light promoted one-pot three-component reactions of isatins, malononitrile, and enolizable C−H activated compounds (2hydroxynaphthalene-1,4-dione, 4-hydroxycoumarine, and dimedone) in the absence of catalyst at room temperature.

Table 1. Optimization of the Reaction Conditions for the Synthesis of Compound 4aa

entry

light source

solvent

time (h)

yield (%)b

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15c 16d 17 18 19 20 21e 22f

white light white light white light white light white light white light white light white light white light white light white light white light white light dark dark dark white light blue light white light (8 W) white light (20 W) white light white light

CH2Cl2 EtOAc H2O CH3CN EtOH EL PEG 400 DMF EtOH/H2O (1:1) EL/H2O (1:1) EL/H2O (2:1) EL/H2O (3:2) EL/H2O (9:1) EL/H2O (3:2) EL/H2O (3:2) EL/H2O (3:2) no EL/H2O (3:2) EL/H2O (3:2) EL/H2O (3:2) EL/H2O (3:2) EL/H2O (3:2)

12 12 12 12 12 12 12 12 12 6 6 6 6 12 6 6 6 6 10 6 5.8 6

trace trace trace 16 20 35 69 71 16 63 71 95 42 trace 26 51 trace 23 90 95 95 96

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RESULTS AND DISCUSSION We commenced our investigation of the visible-light-promoted three-component reaction of isatin, malononitrile, and 2hydroxynaphthalene-1,4-dione under various reaction conditions. Though, this reaction can be carried out in the presence of acids,40,41 tetrabutylammonium bromide (TBAB),42 or metal-containing catalysts.43 As far as we know, the use of a visible-light-promoted reaction in the absence of a catalyst at room temperature has never been reported before. First, a variety of green as well as conventional organic solvents were tested for this three-component reaction under visible light illumination with an 18 W white-light-emitting diode (LED). As demonstrated in Table 1, almost no target product was detected when the reaction mixture was stirring for 12 h in CH2Cl2, EtOAc, and H2O at room temperature in the absence of catalyst (Table 1, entries 1−3). Gratifyingly, the reaction indeed occurred in CH3CN and EtOH, giving desired product 4a in 16% and 20% yields, respectively. The yield of 4a was improved when the reaction was performed in ethyl lactate (EL), PEG 400, or DMF. Further study found that the EL/ H2O solvent system was better for enhancing the yield of the corresponding product. Its ratio of 3:2 was found suitable for this transformation, giving the expected product in almost quantitative yield (95%). A control experiment revealed almost no product was generated when the reaction was performed in the dark at room temperature (entry 14). When the reaction was performed at 50 and 80 °C, the corresponding product 4a was obtained in 26 and 51% yield, respectively. These results indicated that visible light is a critical factor for this reaction in the absence of catalyst conditions. We also tried to optimize the reaction conditions with a variable energy source and intensities of visible light. When the blue light was used as a light source, the product 4a was formed with lower yield (entry 18). The use of an 8 W white LED resulted in a drop in yield to 90% (entry 19). An increase in the intensity of light did not improve the results (entry 20). After confirming the source of light, this model reaction was also investigated with organic dyes such as

a

Experimental conditions: isatin (1 mmol), malononitrile (1 mmol), 2-hydroxynaphthalene-1,4-dione (1.0 mmol), solvent (2 mL), room temperature, under light irradiation (18 W) at room temperature unless otherwise specified in the table. bIsolated yields. cThe reaction was performed at 50 °C. dThe reaction was performed at 80 °C. e Eosin Y (2 mmol %) was added. fThe reaction was carried out on 10 mmol scale.

eosin Y, which was activated by irradiation of visible light. When the reaction was carried out in the presence of eosin Y (2 mmol %), no appreciable effect on the yield or reaction time was observed (entry 21). To further demonstrate the synthetic utility of this methodology, a scale-up reaction was also conducted (10 mmol scale). The model reaction proceeded smoothly under optimized conditions to afford the desired product with the same reaction efficiency, which further highlighted the synthetic advantages of this protocol (entry 22). With the optimized reaction conditions established, various substituted isatins were evaluated under optimized conditions, and the representative results are listed in Table 2. Generally, various isatins bearing electron-rich, electron-neutral, and electron-poor substituents successfully reacted with malononitrile and 2-hydroxynaphthalene-1,4-dione to give the collection of substituted spiro[benzo[g]chromene-4,3′-indoline]-3-carbonitrile with good to excellent yields. Excitingly, the results indicated that Cl, Br, and I substituted on the phenyl ring of isatins were well-tolerated under this reaction, which made further functionalization possible. Intriguingly, the reactions involving the substrates containing a 7-fluoro or 7-trifluoromethyl group successfully generated the desired products 4l and 4o in 89% and 91% yield, respectively. The position of the substituents on the phenyl ring of isatins had little influence on 6176


Research Article

ACS Sustainable Chemistry & Engineering Table 2. Synthesis of Spirooxindole Pyrans Using 2-Hydroxynaphthalene-1,4-dione

a

entry

R1

product

time (h)

yield (%)a

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

H 5-OMe 5-Me 5-F 5-Cl 5-Br 5-I 5-NO2 4-Br 6-Br 7-Me 7-F 7-Cl 7-Br 7-CF3 1-Me

4a 4b 4c 4d 4e 4f 4g 4h 4i 4j 4k 4l 4m 4n 4o 4p

6 6 6 8 4 8 12 4 10 10 10 10 12 12 11 7

95 92 92 91 95 89 83 95 85 82 88 89 87 88 91 94

mp (°C) 298−300 220−222 310−311 312−313 >310 275−276 >310 290−291 >310 >310 >310 >310 309−310 303−305 283−284 270−272

(295)39 (310)39

(275)39 (290)39

(265)32

Isolated yields.

Table 3. Synthesis of Spirooxindole Pyrans Using 4-Hydroxylcoumarin

a

entry

R1

product

time (h)

yield (%)a

mp (°C)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16



4 6 5 5 4 6 9 4 6 10 12 10 12 12 10 7

95 92 94 93 95 90 87 95 89 88 85 86 88 87 88 94

289−290 (283−285)45 308−310 (271−273)45 >310 (>300)45 >310 (306−308)32 >310 (>300)45 >310 (>300)49 >310 (>300)49 >310 (>300)48 >310 >310 (>300)49 >310 (>300)49 >310 >310 (>300)45 >310 >310 285−287 (284−285)45

Isolated yields.

the efficiency of the reaction. The substrate bearing a bromo substituent at the C-4 position on the isatin backbone reacted smoothly and provided the corresponding product 4i in 85% yield. To our satisfaction, the scope of the reaction was further extended to N-protected isatin such as 1-methylisatin, which gave a high yield of 4p (Table 2, entry 16). Encouraged by these results, other enolizable C−H activated compounds such as 4-hydroxylcoumarin and dimedone were

evaluated in this three-component reaction to explore the feasibility of the present protocol. As shown in Tables 3 and 4, all the reactions proceeded very smoothly and provided the respective spiro[indoline-3,4′-pyrano[3,2-c]chromene]-3′-carbonitrile (6) and 5,6,7,8-tetrahydrospiro[chromene-4,3′-indoline]-3-carbonitrile derivatives (8) in high to excellent yields. The present protocol avoids use of acids,44 bases,45−47 metalcontaining catalysts,1 biocatalysts,49,50 heating,51 ultrasound,52 6177


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ACS Sustainable Chemistry & Engineering

tion in a solution to give a cyanoolefin intermediate B with the elimination of water. Then, visible light activated this intermediate to form a free radical intermediate C. Intermediate C abstracted a methylenic hydrogen from malononitrile, generating a malononitrile radical, which in turn abstracts a hydrogen from 2-hydroxynaphthalene-1,4-dione to furnish the intermediate E. Subsequently, intermediate E further reacted with intermediate D, resulting in the form of intermediate F, followed by intramolecular cyclization to yield the desired product 4a. To confirm that the reaction proceeds via radical intermediate, the same reaction was carried out in the presence of hydroquinone as a radical inhibitor. The result showed that only a trace of product 4a was formed. In addition, when the reaction was conducted in the dark at room temperature, no desired product formation was observed. It was also found that no further conversion occurred when the light source was removed, and the reaction could continue when the light was turned on. These controlled experiments indicated that the reaction may proceed through radical pathways.

Table 4. Synthesis of Spirooxindole Pyrans Using Dimedone

entry

R1

product

time (h)

yield (%)a

mp (°C)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16



4 4 4 4 4 5 8 4 8 9 12 10 12 12 12 6

95 92 94 93 96 92 89 95 90 88 84 86 88 89 90 93

288−289 (284−285)50 289−290 (287−289)50 278−280 (280−281)47 270−271 (268−270)44 290−291 (288−290)47 307−308 (306−307)47 >310 (345−347)47 304−305 (302−304)47 >305−307 (>300)51 >310 (>300)51 299−300 (296−297)47 >300 (>300)54 282−283 (280−281)47 305−307 292−293 253−254 (254−256)47

a

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CONCLUSION In summary, we have successfully developed a novel visible light-promoted one-pot three-component reaction of isatins, malononitrile, and enolizable C−H activated compounds for the synthesis of spirooxindole-pyran derivatives. The present protocol improves the existing technologies and avoids the use of any additional promoter and thermal energy. This new process meets all the requirements of green chemistry and opens new doors for the development of more sustainable multicomponent reactions. Further studies focused on expanding the scope of this reaction to the other interesting compounds are ongoing in our laboratory.

Isolated yields.

or microwaves.53 All of the products were isolated in pure form just by washing them with aqueous ethanol followed by recrystallization from ethanol, and no tedious chromatographic purification was needed. On the basis of the above results and literature precedents,2,55,56 a plausible mechanism for this light-promoted three-component reaction is proposed (Scheme 1). First, the intermediate A was formed via tautomerization of malononitrile under irradiation with visible light in the cosolvent (EL/H2O). Intermediate A and isatin underwent Knoevenagel condensa-

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EXPERIMENTAL SECTION

Unless otherwise noted, all reagents were purchased from commercial suppliers and used as received without further purification. Melting points were measured on an X-5 digital melting point apparatus and

Scheme 1. Plausible Reaction Mechanism

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Research Article


2-Amino-6′-bromo-2′,5,10-trioxo-5,10-dihydrospiro[benzo[g]chromene-4,3′-indoline]-3-carbonitrile (4j). Light brown solid; IR (KBr): 3413, 2196, 1734, 1665, 1629, 1605, 1479, 1334, 1302, 1205, 1053, 1027, 1004, 914 cm−1. 1H NMR (500 MHz, DMSO-d6): δ 7.01 (d, J = 1.5 Hz, 1H), 7.10 (dd, J = 8.0, 1.5 Hz, 1H), 7.21 (d, J = 7.5 Hz, 1H), 7.65 (s, 2H), 7.80−7.87 (m, 3H), 8.06 (dd, J = 8.5, 1.5 Hz, 1H), 10.84 (s, 1H) ppm. 13C NMR (125 MHz, DMSO-d6): δ 48.3, 56.7, 112.8, 117.3, 119.3, 122.0, 125.0, 126.5, 126.7, 130.8, 131.0, 134.2, 135.0, 135.3, 135.5, 144.0, 151.1, 159.2, 176.8, 177.9, 182.4 ppm. HRMS (ESI, m/z) calcd. for C21H11BrN3O4 (M + H+): 447.9933. Found: 447.9940. 2-Amino-7′-methyl-2′,5,10-trioxo-5,10-dihydrospiro[benzo[g]chromene-4,3′-indoline]-3-carbonitrile (4k). Light brown solid; IR (KBr): 3435, 3335, 3183, 2205, 1712, 1663, 1631, 1593, 1577, 1401, 1347, 1299, 1200, 1179, 1055, 983 cm−1. 1H NMR (500 MHz, DMSO-d6): δ 2.27 (s, 3H), 6.81 (t, J = 7.5 Hz, 1H), 7.02 (t, J = 7.5 Hz, 2H), 7.55 (s, 2H), 7.82−7.86 (m, 3H), 8.06 (d, J = 7.5 Hz, 1H), 10.71 (s, 1H) ppm. 13C NMR (125 MHz, DMSO-d6): δ 48.7, 57.6, 117.5, 119.2, 120.1, 122.1, 122.3, 126.5, 126.7, 130.7, 130.8, 131.1, 134.7, 134.9, 135.3, 140.7, 150.8, 159.1, 176.9, 178.5, 182.3 ppm. HRMS (ESI, m/z) calcd. for C22H14N3O4 (M + H+): 384.0984. Found: 384.0990. 2-Amino-7′-fluoro-2′,5,10-trioxo-5,10-dihydrospiro[benzo[g]chromene-4,3′-indoline]-3-carbonitrile (4l). Light brown solid; IR (KBr): 3469, 3366, 3272, 2201, 1733, 1667, 1641, 1629, 1591, 1490, 1406, 1340, 1310, 1243, 1231, 1198, 1175, 1052, 1030, 979 cm−1. 1H NMR (500 MHz, DMSO-d6): δ 6.94 (td, J = 7.5, 5.0 Hz, 1H), 7.11− 7.16 (m, 2H), 7.67 (s, 2H), 7.81−7.86 (m, 3H), 7.86 (d, J = 7.5 Hz, 1H), 11.22 (s, 1H) ppm. 13C NMR (125 MHz, DMSO-d6): δ 48.8, 56.9, 116.4 (d, 2JCF = 17.3 Hz), 117.3, 119.4, 120.9, 123.3 (d, 3JCF = 5.7 Hz), 126.5, 126.7, 129.2, 129.3, 130.9 (d, 2JCF = 19.5 Hz), 135.0, 135.3, 137.6, 146.7 (d, 1JCF = 241.0 Hz), 151.0, 159.1, 176.8, 177.8, 182.4 ppm. HRMS (ESI, m/z) calcd. for C21H11FN3O4 (M + H+): 388.0734. Found: 388.0728. 2-Amino-7′-chloro-2′,5,10-trioxo-5,10-dihydrospiro[benzo[g]chromene-4,3′-indoline]-3-carbonitrile (4m). Light brown solid; IR (KBr): 3438, 341, 2204, 1723, 1667, 1633, 1592, 1474, 1455, 1347, 1271, 1202, 1053, 984 cm−1. 1H NMR (500 MHz, DMSO-d6): δ 6.93 (t, J = 7.5 Hz, 1H), 7.23 (d, J = 7.5 Hz, 1H), 7.27 (d, J = 7.5 Hz, 1H), 7.67 (s, 2H), 7.82−7.86 (m, 3H), 8.05 (d, J = 7.0 Hz, 1H), 11.13 (s, 1H) ppm. 13C NMR (125 MHz, DMSO-d6): δ 49.3, 56.8, 114.2, 117.3, 119.4, 123.5, 123.7, 126.5, 126.7, 129.4, 130.8, 131.0, 135.0, 135.3, 135.5, 141.7, 151.0, 159.2, 176.8, 177.9, 182.4 ppm. HRMS (ESI, m/z) calcd. for C21H11ClN3O4 (M + H+): 404.0438. Found: 404.0446. 2-Amino-7′-bromo-2′,5,10-trioxo-5,10-dihydrospiro[benzo[g]chromene-4,3′-indoline]-3-carbonitrile (4n). Light brown solid; IR (KBr): 3443, 3341, 2203, 1724, 1634, 1615, 1592, 1470, 1450, 1413, 1347, 1271, 1201, 1050, 984 cm−1. 1H NMR (500 MHz, DMSO-d6): δ 6.87 (t, J = 7.0 Hz, 1H), 7.26 (d, J = 7.0 Hz, 1H), 7.39 (d, J = 7.0 Hz, 1H), 7.67 (s, 2H), 7.82−7.86 (m, 3H), 8.06 (d, J = 7.0 Hz, 1H), 10.99 (s, 1H) ppm. 13C NMR (125 MHz, DMSO-d6): δ 49.6, 56.9, 102.4, 117.3, 119.4, 124.0, 124.1, 126.5, 126.7, 130.8, 131.0, 132.3, 135.0, 135.3, 135.5, 141.7, 151.0, 159.2, 176.8, 177.9, 182.4 ppm. HRMS (ESI, m/z) calcd. for C21H11BrN3O4 (M + H+): 447.9933. Found: 447.9938. 2-Amino-2′,5,10-trioxo-7′-(trifluoromethyl)-5,10-dihydrospiro[benzo[g]chromene-4,3′-indoline]-3-carbonitrile (4o). Light brown solid; IR (KBr): 3558, 3341, 2199, 1732, 1715, 1669, 1623, 1593, 1458, 1411, 1338, 1303, 1208, 1112, 1082, 1053, 985 cm−1. 1H NMR (500 MHz, DMSO-d6): δ 7.12 (t, J = 7.5 Hz, 1H), 7.52 (d, J = 7.5 Hz, 1H), 7.59 (d, J = 7.0 Hz, 1H), 7.73 (s, 2H), 7.85−7.89 (m, 3H), 8.09 (d, J = 7.5 Hz, 1H), 11.20 (s, 1H) ppm. 13C NMR (125 MHz, DMSOd6): δ 47.7, 56.6, 110.1 (q, 2JCF = 32.4 Hz), 117.1, 119.2, 122.6, 124.1 (q, 1JCF = 272.0 Hz), 125.8, 126.6, 126.7, 128.8 (q, 3JCF = 4.3 Hz), 130.8, 130.9, 135.0, 135.3, 136.6, 139.7, 151.1, 159.3, 176.7, 178.5, 182.4 ppm. HRMS (ESI, m/z) calcd. for C22H11F3N3O4 (M + H+): 438.0702. Found: 438.0708. 2′-Amino-4-bromo-2,5′-dioxo-5′H-spiro[indoline-3,4′-pyrano[3,2-c]chromene]-3′-carbonitrile (6i). White solid; IR (KBr): 3399, 3177, 2208, 1725, 1672, 1614, 1602, 1580, 1448, 1363, 1218, 1178,

are uncorrected. The FT-IR spectra were obtained on a Bruker Tensor 27 Fourier transform infrared spectroscope. NMR spectra of the products were recorded on a Bruker DRX-500 spectrometer (500 MHz for 1H NMR, 125 MHz for 13C NMR) using DMSO as a solvent and TMS as an internal reference. Mass spectra were performed on a 3200 Qtrap instrument with an ESI source. General Procedure for Synthesis of Pyrrolidinones. In a tube equipped with a magnetic stirrer bar, isatin (1 mmol), malononitrile (1 mmol), and active methylene compound (1 mmol) were added in ethyl lactate/water (3:2, 2 mL). The resulting mixture was stirred under irradiation with 18 W white LEDs at room temperature. Upon completion of the reaction (monitored by TLC), the solid precipitate was filtered, followed by washing with aqueous ethanol to obtain the crude product. The crude product was purified by recrystallization from ethanol to obtain the desired pure compounds. Characterization Data for New Products. Light brown solid; IR (KBr): 3441, 3308, 2202, 1718, 1664, 1629, 1593, 1560, 1492, 1337, 1298, 1272, 1205, 1141, 1047, 1026, 983 cm−1. 1H NMR (500 MHz, DMSO-d6): δ 3.62 (s, 3H), 6.74−6.78 (m, 2H), 6.92 (d, J = 2.0 Hz, 1H), 7.54 (s, 2H), 7.79−7.87 (m, 3H), 8.06 (d, J = 8.5 Hz, 1H), 10.47 (s, 1H) ppm. 13C NMR (125 MHz, DMSO-d6): δ 49.0, 55.9, 57.6, 110.4, 111.5, 114.1, 117.5, 119.9, 126.5, 126.7, 130.8, 131.1, 134.9, 135.3, 135.4, 136.2, 151.0, 155.6, 159.0, 177.0, 178.0, 182.2 ppm. HRMS (ESI, m/z) calcd. for C22H14N3O5 (M + H+): 400.0933. Found: 400.0939. 2-Amino-5′-fluoro-2′,5,10-trioxo-5,10-dihydrospiro[benzo[g]chromene-4,3′-indoline]-3-carbonitrile (4d). Light brown solid; IR (KBr): 3455, 3343, 2203, 1731, 1629, 1577, 1457, 1415, 1289, 1237, 1270, 1205, 1183, 984 cm−1. 1H NMR (500 MHz, DMSO-d6): δ 6.86 (dd, J = 8.0, 4.5 Hz, 1H), 7.02 (td, J = 8.0, 2.5 Hz, 1H), 7.22 (dd, J = 8.0, 2.5 Hz, 1H), 7.63 (s, 2H), 7.80−7.87 (m, 3H), 8.06 (d, J = 7.0 Hz, 1H), 10.69 (s, 1H) ppm. 13C NMR (125 MHz, DMSO-d6): δ 49.0, 56.9, 110.7 (d, 3JCF = 7.8 Hz), 112.6 (d, 2JCF = 24.8 Hz), 115.6 (d, 2JCF = 23.2 Hz), 117.3, 119.4, 126.5, 126.7, 130.8, 131.0, 135.0, 135.3, 136.5 (d, 3JCF = 7.6 Hz), 138.4 (d, 4JCF = 1.4 Hz), 151.0, 158.6 (d, 1JCF = 235.6 Hz), 159.1, 176.8, 178.0, 182.3 ppm. HRMS (ESI, m/z) calcd. for C21H11FN3O4 (M + H+): 388.0734. Found: 388.0739. 2-Amino-5′-chloro-2′,5,10-trioxo-5,10-dihydrospiro[benzo[g]chromene-4,3′-indoline]-3-carbonitrile (4e). Light brown solid; IR (KBr): 3460, 3372, 2212, 1726, 1735, 1652, 1596, 1476, 1408, 1336, 1288, 1223, 1203, 1124, 1065, 981 cm−1. 1H NMR (500 MHz, DMSO-d6): δ 6.85 (d, J = 8.5 Hz, 1H), 7.22 (dd, J = 8.5, 2.0 Hz, 1H), 7.37 (d, J = 2.0 Hz, 1H), 7.62 (s, 2H), 7.78−7.85 (m, 3H), 8.03 (d, J = 7.5 Hz, 1H), 10.78 (s, 1H) ppm. 13C NMR (125 MHz, DMSO-d6): δ 48.7, 56.8, 111.4, 117.3, 119.2, 125.0, 126.4, 126.5, 126.7, 129.2, 130.9, 131.0, 135.0, 135.3, 136.8, 141.1, 151.2, 159.2, 176.8, 177.8, 182.4 ppm. HRMS (ESI, m/z) calcd. for C21H11ClN3O4 (M + H+): 404.0438. Found: 404.0431. 2-Amino-5′-iodo-2′,5,10-trioxo-5,10-dihydrospiro[benzo[g]chromene-4,3′-indoline]-3-carbonitrile (4g). Light brown solid; IR (KBr): 3445, 3390, 2986, 2223, 1748, 1691, 1645, 1611, 1474, 1450, 1356, 1317, 1218, 1132, 1087, 1039, 997 cm−1. 1H NMR (500 MHz, DMSO-d6): δ 6.75 (d, J = 8.0 Hz, 1H), 7.55 (d, J = 8.0 Hz, 1H), 7.65 (s, 1H), 7.67 (s, 2H), 7.85−7.89 (m, 3H), 8.08 (d, J = 7.5 Hz, 1H), 10.82 (s, 1H) ppm. 13C NMR (125 MHz, DMSO-d6): δ 48.5, 56.9, 112.5, 117.4, 119.2, 126.5, 126.7, 130.9, 131.0, 133.1, 135.0, 135.3, 137.4, 137.8, 142.0, 151.2, 159.1, 175.0, 177.5, 182.4 ppm. HRMS (ESI, m/z) calcd. for C21H11IN3O4 (M + H+): 495.9794. Found: 495.9788. 2-Amino-4′-bromo-2′,5,10-trioxo-5,10-dihydrospiro[benzo[g]chromene-4,3′-indoline]-3-carbonitrile (4i). Light brown solid; IR (KBr): 3430, 3169, 2209, 1721, 1671, 1633, 1609, 1593, 1443, 1407, 1338, 1293, 1205, 1058, 1045, 796 cm−1. 1H NMR (500 MHz, DMSO-d6): δ 6.96 (d, J = 8.0 Hz, 1H), 7.14 (d, J = 8.0 Hz, 1H), 7.22 (t, J = 7.5 Hz, 1H), 7.77 (s, 2H), 7.88−7.91 (m, 3H), 8.09 (d, J = 7.0 Hz, 1H), 11.10 (s, 1H) ppm. 13C NMR (125 MHz, DMSO-d6): δ 50.1, 54.4, 109.9, 117.1, 118.7, 119.0, 125.9, 126.7, 127.0, 130.5, 130.6, 130.9, 131.5, 135.3, 135.7, 144.5, 151.5, 160.1, 176.6, 177.0, 182.1 ppm. HRMS (ESI, m/z) calcd. for C21H10BrN3O4 (M + H+): 447.9933. Found: 447.9939. 6179



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1119, 1093, 1080, 1074, 973 cm−1. 1H NMR (500 MHz, DMSO-d6): δ 6.93 (d, J = 7.5 Hz, 1H), 7.13 (d, J = 7.5 Hz, 1H), 7.22 (d, J = 7.5 Hz, 1H), 7.55 (t, J = 7.5 Hz, 1H), 7.58 (d, J = 7.5 Hz, 1H), 7.81 (t, J = 7.5 Hz, 1H), 7.84 (s, 2H), 7.97 (d, J = 7.5 Hz, 1H), 11.00 (s, 1H) ppm. 13 C NMR (125 MHz, DMSO-d6): δ 49.7, 54.6, 100.1, 109.8, 112.4, 117.1, 117.3, 118.9, 123.2, 125.8, 126.0, 129.6, 131.6, 134.6, 144.9, 152.6, 156.4, 158.6, 160.1, 176.7 ppm. HRMS (ESI, m/z) calcd. for C20H11BrN3O4 (M + H+): 435.9933. Found: 435.9940. 2′-Amino-7-fluoro-2,5′-dioxo-5′H-spiro[indoline-3,4′-pyrano[3,2c]chromene]-3′-carbonitrile (6l). White solid; IR (KBr): 3297, 2196, 1747, 1728, 1667, 1610, 1596, 1610, 1494, 1470, 1358, 1328, 1218, 1911, 1114, 1000, 991 cm−1. 1H NMR (500 MHz, DMSO-d6): δ 6.96−7.00 (m, 1H), 7.14 (d, J = 7.5 Hz, 1H), 7.17 (t, J = 7.5 Hz, 1H), 7.52 (d, J = 7.5 Hz, 1H), 7.57 (t, J = 7.5 Hz, 1H), 7.77−7.81 (m, 3H), 7.96 (t, J = 7.5 Hz, 1H), 11.23 (s, 1H) ppm. 13C NMR (125 MHz, DMSO-d6): δ 48.4, 57.0, 101.4, 112.9, 116.5 (d, 2JCF = 17.1 Hz), 117.2, 117.3, 120.8 (d, 3JCF = 7.6 Hz), 123.2, 123.4 (d, 3JCF = 5.5 Hz), 125.6, 129.7 (d, 2JCF = 12.3 Hz), 134.3, 136.3 (d, 4JCF = 3.6 Hz), 146.6 (d, 1 JCF = 240.0 Hz), 152.6, 155.7, 158.8, 158.9, 177.5 ppm. HRMS (ESI, m/z) calcd. for C20H11FN3O4 (M + H+): 376.0734. Found: 376.0728. 2′-Amino-7-bromo-2,5′-dioxo-5′H-spiro[indoline-3,4′-pyrano[3,2-c]chromene]-3′-carbonitrile (6n). White solid; IR (KBr): 3322, 2197, 1705, 1667, 1629, 1611, 1595, 1474, 1357, 1323, 1223, 1130, 1114, 1087, 975 cm−1. 1H NMR (500 MHz, DMSO-d6): δ: 6.92 (t, J = 8.0 Hz, 1H), 7.28 (d, J = 7.0 Hz, 1H), 7.43 (d, J = 8.0 Hz, 1H), 7.52 (d, J = 8.5 Hz, 1H), 7.56 (t, J = 7.5 Hz, 1H), 7.79 (t, J = 8.5 Hz, 3H), 7.96 (d, J = 7.0 Hz, 1H), 11.02 (s, 1H) ppm. 13C NMR (125 MHz, DMSO-d6): δ 49.2, 57.0, 101.5, 102.4, 113.0, 117.2, 117.3, 123.2, 123.9, 124.3, 125.6, 132.4, 134.3, 135.2, 142.2, 152.6, 155.7, 158.9, 159.0, 177.6 ppm. HRMS (ESI, m/z) calcd. for C20H11BrN3O4 (M + H+): 435.9933. Found: 435.9938. 2′-Amino-2,5′-dioxo-7-(trifluoromethyl)-5′H-spiro[indoline-3,4′pyrano[3,2-c]chromene]-3′-carbonitrile (6o). White solid; IR (KBr): 3384, 3187, 2208, 1727, 1673, 1626, 1613, 1460, 1362, 1342, 1216, 1169, 1117, 1086, 979 cm−1. 1H NMR (500 MHz, DMSO-d6): δ 7.14 (t, J = 7.5 Hz, 1H), 7.51−7.56 (m, 2H), 7.59 (t, J = 7.5 Hz, 1H), 7.79 (d, J = 7.5 Hz, 2H), 7.82 (s, 2H), 7.97 (d, J = 7.5 Hz, 1H), 11.19 (s, 1H) ppm. 13C NMR (125 MHz, DMSO-d6): δ 47.4, 56.7, 101.2, 110.9 (q, 2JCF = 32.0 Hz), 112.9, 117.1, 117.2, 122.7, 123.2, 124.1 (q, 1JCF = 272.0 Hz), 125.6, 126.0 (q, 3JCF = 4.7 Hz), 128.8, 134.4, 135.3, 140.1, 152.6, 156.0, 158.9, 159.1, 178.2 ppm. HRMS (ESI, m/z) calcd. for C21H11F3N3O4 (M + H+): 426.0702. Found: 426.0695. 2-Amino-7′-bromo-7,7-dimethyl-2′,5-dioxo-5,6,7,8tetrahydrospiro[chromene-4,3′-indoline]-3-carbonitrile (8n). White solid; IR (KBr): 3371, 3308, 3157, 2193, 1732, 1680, 1600, 1449, 1348, 1322, 1220, 1210, 1163, 1137, 1052, 772 cm−1. 1H NMR (500 MHz, DMSO-d6): δ 1.01 (s, 3H), 1.04 (s, 3H), 2.10−2.22 (m, 2H), 2.51−2.62 (m, 2H), 6.87 (t, J = 8.0 Hz, 1H), 7.02 (d, J = 7.5 Hz, 1H), 7.35 (s, 3H), 10.73 (s, 1H) ppm. 13C NMR (125 MHz, DMSO-d6): δ 27.5, 28.0, 32.5, 48.4, 50.4, 57.4, 102.2, 111.0, 117.7, 122.8, 123.9, 131.6, 136.6, 142.0, 159.3, 165.0, 178.4, 195.5 ppm. HRMS (ESI, m/z) calcd. for C19H17BrN3O3 (M + H+): 414.0453. Found: 414.0446. 2-Amino-7,7-dimethyl-2′,5-dioxo-7′-(trifluoromethyl)-5,6,7,8tetrahydrospiro[chromene-4,3′-indoline]-3-carbonitrile (8o). White solid; IR (KBr): 3358, 3294, 3180, 2959, 2195, 1737, 1682, 1624, 1603, 1454, 1488, 1416, 1372, 1350, 1317, 1197, 1135, 1117, 1066, 1052, 794 cm−1. 1H NMR (500 MHz, DMSO-d6): δ 1.02 (s, 3H), 1.04 (s, 3H), 2.13 and 2.19 (AB system, J = 16.0 Hz, 2H), 2.53 and 2.61 (AB system, J = 17.5 Hz, 2H), 7.09 (t, J = 7.5 Hz, 1H), 7.33 (d, J = 7.5 Hz, 1H), 7.40 (s, 2H), 7.45 (d, J = 7.5 Hz, 1H), 10.90 (s, 1H) ppm. 13 C NMR (125 MHz, DMSO-d6): δ 27.6, 27.9, 32.5, 46.0, 50.3, 57.1, 110.6 (q, 2JCF = 32.0 Hz), 110.8, 117.5, 122.3, 124.2 (q, 1JCF = 272.0 Hz), 125.2 (q, 3JCF = 4.3 Hz), 125.3, 127.6, 136.7, 140.0, 159.4, 165.2, 179.0, 195.5 ppm. HRMS (ESI, m/z) calcd. for C20H17F3N3O3 (M + H+): 404.1222. Found: 404.1230.

Research Article

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.7b01102. Spectra data and copies of 1H NMR and 13C NMR spectra of all compounds (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*Fax: +86-311-80787431. E-mail: [email protected] *Fax: +86-311-80787431. E-mail: [email protected]. ORCID

Zhan-Hui Zhang: 0000-0002-1082-5773 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS Financial support from the National Natural Science Foundation of China (No. 21272053) and the Natural Science Foundation of Hebei Province (No. B2015205182) is gratefully acknowledged.

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REFERENCES

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