Diazenylation

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Cite This: J. Org. Chem. 2018, 83, 11956−11962

Copper(II)-Catalyzed Four-Component Oxysulfonylation/ Diazenylation: Synthesis of α‑Arylhydrazo-β-keto Sulfones Wen-Chao Gao,*,† Yu-Fei Cheng,† Yu-Zhu Shang,† Hong-Hong Chang,† Xing Li,† Rong Zhou,*,† Yan Qiao,‡ and Wen-Long Wei‡ †

College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, P. R. China State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, P. R. China

‡

J. Org. Chem. 2018.83:11956-11962. Downloaded from pubs.acs.org by UNIV OF SUNDERLAND on 10/05/18. For personal use only.

S Supporting Information *

ABSTRACT: A new and convenient method for one-pot synthesis of α-arylhydrazo-β-keto sulfones is developed via Cu (II)-catalyzed oxysulfonylation/diazenylation of alkenes. This four-component cascade reaction enables a series of αarylhydrazo-β-keto sulfone derivatives accessed from readily available alkenes, sulfinates, and diazonium salts under aerobic conditions. Furthermore, the 3-sulfonyl cinnolin-4(1H)-one skeleton is successfully constructed from the corresponding α-arylhydrazo-β-keto sulfone product under basic conditions.

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Scheme 1. Different Methods for the Synthesis of αHydrazo, -Aryl, and -Sulfonyl Ketones

INTRODUCTION As an important class of compounds in organic chemistry, hydrazone and its derivatives are usually encountered in both laboratories and industry to synthetic building blocks,1 pharmaceutical agents,2 and chelating molecules toward metal ions.3 Traditionally, hydrazones are prepared from the condensation of hydrazines with carbonyl compounds under neutral or acidic conditions.4 Since α-hydrazo ketone derivatives are good candidates for the construction of indoles (Fischer indole synthesis) as well as amino acids,5 another frequently used method to construct hydrazones especially for α-hydrazo ketone derivatives is the coupling of diazonium salts with 1,3-dicarbonyl compounds that was known as the Japp− Klingemann reaction (Scheme 1, eq 1).6a Although Japp− Klingemann-type coupling for α-hydrazo ketone construction has been extensively studied for several decades,6b−e the synthesis of α-hydrazo ketone derivatives from simple and unactivated alkenes would be more convenient but unexplored.7 Methods for mild and selective diversification of alkenes have elicited strong interest in the synthetic community since they provide a powerful platform to access structurally complex molecules from common and simple starting materials.8 Specifically, radical oxysulfonylation and oxyarylation of alkenes via direct aerobic oxidation offer facile and efficient strategies for the synthesis of β-keto sulfones and α-aryl ketones (Scheme 1, eqs 2 and 3).9 Significant progress has been achieved for oxygenation of alkenes via Cu-catalyzed dioxygen activation, examples of which include the noteworthy works of Lei,10 Jiang,11 Jiao,12 Wang,9a and Heinrich.9d We were therefore motivated to investigate if the Cu-catalyzed radical activation and oxygenation of alkenes could access αaryl-β-keto sulfones with the utility of both sulfonyl and aryl radical precursors.13 However, the desired α-aryl-β-keto sulfones through radical oxysulfonation/arylation were not © 2018 American Chemical Society

detected, and α-hydrazo-β-keto sulfones were isolated as the major products (Scheme 1, eq 4). Herein, we would like to present this unexpected four-component reaction for one-pot synthesis of α-hydrazo-β-keto sulfones via Cu (II)-catalyzed radical oxysulfonylation of alkenes and subsequent diazenylation of β-keto sulfones, by employing alkenes, diazonium salts, and sulfinates under aerobic conditions.

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RESULTS AND DISCUSSION Our investigation started with the 4-methoxyphenyl diazonium salt (1a), sodium toluenesulfinate (2a), and styrene (3a) as Received: July 18, 2018 Published: September 5, 2018 11956

DOI: 10.1021/acs.joc.8b01843 J. Org. Chem. 2018, 83, 11956−11962

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The Journal of Organic Chemistry

Table 2. Scope of Alkenes for the One-Pot Synthesis of αArylhydrazo-β-keto Sulfonesa

substrates under air atmosphere, and the representative results are listed in Table 1. No product was detected in the absence Table 1. Brief Survey on Reaction Conditionsa

a

Reaction conditions: 1a (0.2 mmol), 2a (0.4 mmol), 3a (1 mmol), catalyst (20 mol %), in 1 mL of solvent, under air atmosphere for 6−8 h. bIsolated yield of 4a. c2a was replaced by 2b. d2a was replaced by 2c.

a

of catalysts in DMA (entry 1). When copper(II) catalysts were employed in the reaction system, the desired α-hydrazo-β-keto sulfone 4a was obtained as the major product (entries 3−6). To our delight, the yield of 4a was increased to 80% using CuSO4·5H2O as the catalyst (entry 6). Attempts to increase or lower the reaction temperature resulted in the decrease in reaction efficiency (entries 7 and 8). Other solvents, such as CH2Cl2, DMF, CH3CN, C2H5OH, H2O, and DMSO were proved to be not effective (entries 9−14). Furthermore, two sulfonylating reagents, sulfonylhydrazide 2b and sulfinic acid 2c, which were commonly used in radical sulfonylation of alkenes,9a,10 were also examined in this transformation. Unfortunately, the desired product 4a was not detected, whereas 1-phenyl-2-(phenylsulfonyl)ethanone was isolated as the major product instead (entries 15 and 16). With the optimal conditions in hand, the scope and limitations of this Cu (II)-catalyzed four-component reaction was subsequently investigated using different alkenes, sulfinates, and diazonium salts (Table 2 and Table 3). A series of styrene derivatives with different substituents were first subjected to the optimal reaction conditions. Both electron-donating groups, including 4-methyl (4b) and 4methoxyl (4c), and electron-withdrawing groups such as chloro (4d), bromo (4e and 4f), and fluoro (4g-i) groups on the phenyl ring of alkenes were well tolerated, readily

affording the corresponding products in good yields. Moreover, the location of the substituents on the phenyl ring only had a slight influence on the reaction yields (4e vs 4f, and 4h vs 4i). To our delight, the X-ray single crystal structure of 4d was obtained to further confirm the product exclusively in the hydrazone form rather than azo form.7,14 Other aromatic rings like naphthyalene were also suitable for this transformation, and the desired product 4j was furnished in 67% yield. However, when hex-1-ene or β-methylstyrene was employed as the substrate, the corresponding α-hydrazo-β-keto sulfone 4k or 4l was not detected. Furthermore, two naturally derived alkenes from L-tyrosine and coumarin also performed well under the standard conditions, giving the corresponding products in moderate to high yields (4m and 4n). Next, the scope of sulfinates and diazonium salts were examined. As shown in Table 3, various sodium sulfinates bearing electron-donating (OMe and t-Bu) or -withdrawing (F and CF3) groups on the phenyl ring could be smoothly converted to the corresponding products in moderate to good yields (4o−s). Other aromatic systems such as the thienyl and naphthyl rings could be also tolerated in this transformation, delivering the corresponding products in moderate yields. Moreover, sodium methanesulfinate was a good sulfonyl source for this reaction, and the product 4v was obtained in 64% yield. In addition, several aryl diazonium salts with

Reaction conditions: 1a (0.2 mmol), 2a (0.4 mmol), 3 (1 mmol), and CuSO4·5H2O (20 mol %), in DMA (1 mL), stirred at room temperature under air atmosphere.

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DOI: 10.1021/acs.joc.8b01843 J. Org. Chem. 2018, 83, 11956−11962

Article

The Journal of Organic Chemistry Table 3. Scope of Sulfinates and Diazonium Salts for the One-Pot Synthesis of α-Arylhydrazo-β-keto Sulfonesa

Scheme 3. Control Experiments

sulfone 4a could be isolated in 71% yield when treating the mixture of 6 and 1a with 1.0 equiv of TsNa and 20 mol % of CuSO4·5H2O (Scheme 3, eqs 3 and 4). These results indicated that β-keto sulfone 6 was a key intermediate for the generation of 4a and that the combination of TsNa with CuSO4·5H2O was necessary for the diazenylation step. According to these results and literature reports, a plausible mechanism was proposed in Scheme 4. Initially, in the

a

Reaction conditions: 1 (0.2 mmol), 2 (0.4 mmol), 3a (1 mmol), and CuSO4·5H2O (20 mol %), in DMA (1 mL), stirred at room temperature under air atmosphere.

Scheme 4. Proposed Mechanism for the Formation of Compound 4

different substituents on the phenyl ring also proceeded smoothly and provided the products 4w−y in moderate yields. As an important heterocycle, the cinnoline skeleton is found in many drugs (e.g., Cinoxacin) and reported to have a wide range of pharmacological applications.15 With the product 4j derived from 2-fluorostyrene in hand, a base-promoted intramolecular cyclization could smoothly proceed to afford the 3-sulfonylated cinnolin-4(1H)-one 5 in 60% yield (Scheme 2). Therefore, our methodology has also offered an alternative way to 3-sulfonylated cinnoline derivatives. Scheme 2. Synthesis of 3-Sulfonylated Cinnolin-4(1H)-one Skeleton from 4j

presence of Cu (II) catalyst, sulfonyl anion 2 was oxidized via a single electron transfer (SET) process by dioxygen,16 affording oxygen centered radical I, which could resonate to sulfonyl radical II. The addition of sulfonyl radical II to the C−C double bond produced benzyl radical III, which interacted with O2 to afford peroxy radical IV. Cu (II)-peroxyl intermediate V was then generated via radical coupling,11,12 and it subsequently decomposed to β-keto sulfone VI by elimination of [Cu(OH)]+.17 Thereafter, in the presence of CuSO4·5H2O and sodium sulfinates, β-keto sulfone VI was continuously converted to an enol Cu (II) intermediate VII, which underwent diazenylation by the coupling with diazonium salts to produce intermediate VIII. Finally, the tautomerization of VIII led to product 4.

In order to gain insight into the reaction mechanism of the formation of compounds 4, we performed several control experiments. First, this transformation was completely inhibited in the presence of a catalytic amount of the radical inhibitor 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) (Scheme 3, eq 1). Under the standard reaction conditions but without diazonium salts, the reaction of 3a with 2a only gave 1-phenyl-2-(phenylsulfonyl)ethanone (6) in 90% yield (Scheme 3, eq 2). However, β-keto sulfone 6 failed to couple with diazonium salt 1a to give 4a in the absence of TsNa or CuSO4·5H2O, whereas the desired α-arylhydrazo-β-keto 11958

DOI: 10.1021/acs.joc.8b01843 J. Org. Chem. 2018, 83, 11956−11962

Article

The Journal of Organic Chemistry

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21.7, 21.6. HRMS (ESI) m/z calcd for C23H23N2O4S [M + H]+: 423.1373; found, 423.1375. (Z)-1-(4-Methoxyphenyl)-2-(2-(4-methoxyphenyl)hydrazono)-2tosylethanone (4c). Yield: 63.0 mg (72%); time, 6 h; yellow solid; mp 235−237 °C; TLC, Rf = 0.33 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.35 (s, 1H), 8.03 (d, 2H, J = 8.4 Hz), 7.84 (d, 2H, J = 8.8 Hz), 7.36 (d, 2H, J = 8.0 Hz), 7.14 (d, 2H, J = 8.8 Hz), 6.90 (dd, 4H, J = 8.8 Hz, J = 2.4 Hz), 3.87 (s, 3H), 3.81 (s, 3H), 2.43 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 184.9, 162.9, 157.3, 145.1, 137.8, 135.2, 132.5, 129.6, 128.5, 116.7, 115.0, 113.1, 55.6, 55.4, 21.7. HRMS (ESI) m/z calcd for C23H23N2O5S [M + H]+: 439.1322; found, 439.1335. (Z)-1-(4-Chlorophenyl)-2-(2-(4-methoxyphenyl)hydrazono)-2-tosylethanone (4d). Yield: 60.0 mg (68%); time, 8 h; yellow solid; mp 158−160 °C; TLC, Rf = 0.35 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.48 (s, 1H), 8.03 (d, 2H, J = 8.4 Hz), 7.72 (d, 2H, J = 8.4 Hz), 7.37 (t, 4H, J = 8.4 Hz), 7.12 (d, 2H, J = 9.2 Hz), 6.92 (d, 2H, J = 8.8 Hz), 3.82 (s, 3H), 2.44 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 185.2, 157.6, 145.4, 138.3, 137.5, 135.7, 134.9, 131.5, 129.6, 128.6, 128.1, 116.9, 115.0, 55.6, 21.7. HRMS (ESI) m/z calcd for C22H20ClN2O4S [M + H]+: 443.0826; found, 443.0831. (Z)-1-(4-Bromophenyl)-2-(2-(4-methoxyphenyl)hydrazono)-2-tosylethanone (4e). Yield: 68.0 mg (70%); time, 10 h; yellow solid; mp 202−204 °C; TLC, Rf = 0.30 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.49 (s, 1H), 8.03 (d, 2H, J = 8.4 Hz), 7.65 (d, 2H, J = 8.4 Hz), 7.54 (d, 2H, J = 8.4 Hz), 7.37 (d, 2H, J = 5.2 Hz), 7.12 (d, 2H, J = 9.2 Hz), 6.92 (d, 2H, J = 8.8 Hz), 3.82 (s, 3H), 2.44 (s, 3H). 13 C NMR (CDCl3, 100 MHz): δ 185.3, 157.6, 145.4, 137.4, 136.2, 134.8, 131.6, 131.0, 129.6, 128.6, 127.9, 126.9, 116.9, 115.0, 55.6, 21.7. HRMS (ESI) m/z calcd for C22H20BrN2O4S [M + H]+: 487.0322, 489.0302; found, 487.0328, 489.0308. (Z)-1-(3-Bromophenyl)-2-(2-(4-methoxyphenyl)hydrazono)-2-tosylethanone (4f). Yield: 69.2 mg (71%); time, 7 h; yellow solid; mp 149−151 °C; TLC, Rf = 0.33 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.52 (s, 1H), 8.03 (d, 2H, J = 8.4 Hz), 7.94 (s, 1H), 7.70−7.61 (m, 2H), 7.37 (d, 2H, J = 8.0 Hz), 7.30 (d, 1H, J = 8.0 Hz), 7.15 (d, 2H, J = 9.2 Hz), 6.92 (d, 2H, J = 9.2 Hz), 3.82 (s, 3H), 2.44 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 184.7, 157.7, 145.4, 139.2, 137.3, 134.8, 134.6, 133.2, 129.6, 129.4, 128.63, 128.53, 121.7, 117.0, 115.0, 55.6, 21.7. HRMS (ESI) m/z calcd for C22H20BrN2O4S [M + H]+: 487.0322, 489.0302; found, 487.0328, 489.0306. (Z)-1-(4-Fluorophenyl)-2-(2-(4-methoxyphenyl)hydrazono)-2-tosylethanone (4g). Yield: 59.6 mg (70%); time, 5.5 h; yellow solid; mp 187−189 °C; TLC, Rf = 0.36 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.45 (s, 1H), 8.03 (d, 2H, J = 8.4 Hz), 7.85− 7.78 (m, 2H), 7.37 (d, 2H, J = 8.0 Hz), 7.15−7.05 (m, 4H), 6.91 (d, 2H, J = 9.2 Hz), 3.81 (s, 3H), 2.44 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 185.0, 165.0 (d, J = 272.0 Hz), 157.6, 145.3, 137.6, 134.9, 133.5 (d, J = 3.1 Hz), 132.6 (d, J = 8.9 Hz), 129.6, 128.6, 116.9, 115.0, 114.8, 55.6, 21.7. 19F NMR (CDCl3, 376 MHz): δ −102.65. HRMS (ESI) m/z calcd for C22H20FN2O4S [M + H]+: 427.1122; found, 427.1120. (Z)-1-(3-Fluorophenyl)-2-(2-(4-methoxyphenyl)hydrazono)-2-tosylethanone (4h). Yield: 61.4 mg (72%); time, 6 h; yellow solid; mp 131−133 °C; TLC, Rf = 0.33 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.51 (s, 1H), 8.04 (d, 2H, J = 8.4 Hz), 7.56 (d, 1H, J = 7.6 Hz), 7.49−7.45 (m, 1H), 7.42−7.35 (m, 3H), 7.25−7.18 (m, 1H), 7.13 (d, 2H, J = 8.8 Hz), 6.91 (d, 2H, J = 9.2 Hz), 3.82 (s, 3H), 2.45 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 185.0, 157.7, 145.4, 136.1 (d, J = 256.3 Hz), 129.6, 129.3 (d, J = 7.5 Hz), 128.6, 125.8 (d, J = 2.9 Hz), 118.8 (d, J = 21.0 Hz), 117.0, 116.9 (d, J = 22.9 Hz), 115.0, 55.6, 21.8. 19F NMR (CDCl3, 376 MHz): δ −112.95. HRMS (ESI) m/z calcd for C22H20FN2O4S [M + H]+: 427.1122; found, 427.1117. (Z)-1-(2-Fluorophenyl)-2-(2-(4-methoxyphenyl)hydrazono)-2-tosylethanone (4i). Yield: 62.2 mg (73%); time, 11 h; yellow solid; mp 153−155 °C; TLC, Rf = 0.31 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.47 (s, 1H), 8.03(d, 2H, J = 8.4 Hz), 7.47−7.41 (m, 2H), 7.37 (d, 2H, J = 8.4 Hz), 7.18 (t, 1H, J = 7.6 Hz), 7.08 (d, 1H, J = 8.8 Hz), 7.02 (d, 2H, J = 8.8 Hz), 6.85 (d, 2H, J = 8.8 Hz), 3.79 (s, 3H), 2.44 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 185.1, 159.6 (d, J

CONCLUSION In summary, we have developed a copper-catalyzed fourcomponent reaction by employing alkenes, sodium sulfinates, diazonium salts, and dioxygen, through radical oxysulfonylation and diazenylation to access α-arylhydrazo-β-keto sulfones. Notably, this transformation exhibits a broad range of functional-group tolerance and enables the formation of C− O, C−S, and C−N bonds in one pot. Furthermore, the conversion of α-arylhydrazo-β-keto sulfone 4j to 3-sulfonylated cinnolin-4(1H)-one is readily realized. Efforts toward further mechanistic details and other synthetic applications are underway.

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EXPERIMENTAL SECTION

General Information. NMR spectra were recorded using 400 MHz NMR spectrometers with CDCl3 as the deuterated solvent, and the resonances of proton, carbon, and fluorine were at 400, 100, and 376 MHz, respectively. Chemical shifts (δ) were reported in ppm and referenced to the deuterated chloroform (1H, δ = 7.26 ppm; 13C, δ = 77.00 ppm). High-resolution mass spectrometry (HRMS) was carried out on a TOF-Q spectrometer instrument with an ESI source. Melting points were measured with a RD-II type melting point apparatus (uncorrected). X-ray structural analysis was obtained with an X-ray single-crystal diffractometer. Solvents, unless otherwise noted, were purified according to standard procedures before use. Column chromatography was performed on silica gel (200−300 mesh) by using EtOAc and PE (petroleum ether) as eluent. PE, where used, has the boiling point range of 60−90 °C. Typical Procedure for the Preparation of Diazonium Salts. To BF3·Et2O (1.06 g, 7.50 mmol, 1.50 equiv) contained in a three-necked round-bottomed flask fitted with two addition funnels was slowly added 5.0 mmol of the aromatic amine in 10.0 mL of anhydrous THF at 0 °C in an ice−water bath. t-BuONO (0.618 g, 6.00 mmol, 1.20 equiv) in 5.00 mL of anhydrous THF was then added dropwise to the above rapidly stirred reaction solution. The reaction mixture was stirred for 30 min, and then n-hexane (40 mL) was added. The formed precipitate was suction filtered, washed with cold ether (10 mL × 2), and dried under reduced pressure at room temperature to give the desired diazonium salt. Typical Procedure for the Synthesis of α-Arylhydrazo-β-keto Sulfones. To a mixture of styrene (1.0 mmol), sodium toluenesulfinate (0.4 mmol), and 4-methoxyphenyl diazonium salt (0.2 mmol), CuSO4·5H2O (0.04 mmol, 20 mol %) and DMA (1 mL) were added in a 10 mL round-bottomed flask at room temperature under air atmosphere. The reaction vessel was allowed to stir at room temperature until the starting material was consumed. After the reaction, the resulting mixture was diluted with EtOAc (30 mL), washed with H2O (10 mL × 3), dried with Na2SO4, and concentrated under vacuum. The residue was purified by column chromatography (eluent: PE/EtOAc = 4:1) to give the desired 4a. (Z)-2-(2-(4-Methoxyphenyl)hydrazono)-1-phenyl-2-tosylethanone (4a). Yield: 64.0 mg (80%); time, 7 h; yellow solid; mp 184− 186 °C; TLC, Rf = 0.34 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.45 (s, 1H), 8.04 (d, 2H, J = 8.4 Hz), 7.77 (d, 2H, J = 8.4 Hz), 7.52 (t, 1H, J = 7.2 Hz), 7.43−7.34 (m, 4H), 7.12 (d, 2H, J = 8.8 Hz), 6.89 (d, 2H, J = 9.2 Hz), 3.81 (s, 3H), 2.44 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 186.5, 157.4, 145.2, 137.6, 137.4, 135.0, 131.9, 130.1, 129.6, 128.6, 127.7, 116.9, 114.9, 55.6, 21.7. HRMS (ESI) m/z calcd for C22H21N2O4S [M + H]+: 409.1216; found, 409.1218. (Z)-2-(2-(4-Methoxyphenyl)hydrazono)-1-(p-tolyl)-2-tosylethanone (4b). Yield: 64.2 mg (76%); time, 7 h; yellow solid; mp 182− 184 °C; TLC, Rf = 0.32 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.43 (s, 1H), 8.03 (d, 2H, J = 8.4 Hz), 7.71 (d, 2H, J = 8.0 Hz), 7.36 (d, 2H, J = 8.0 Hz), 7.20 (d, 2H, J = 8.0 Hz), 7.14 (d, 2H, J = 9.2 Hz), 6.90 (d, 2H, J = 8.8 Hz), 3.81 (s, 3H), 2.43 (s, 3H), 2.41 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 186.0, 157.3, 145.1, 142.7, 137.7, 135.1, 134.6, 130.3, 129.6, 128.53, 128.47, 116.8, 114.9, 55.6, 11959

DOI: 10.1021/acs.joc.8b01843 J. Org. Chem. 2018, 83, 11956−11962

Article

The Journal of Organic Chemistry

(Z)-2-((4-Fluorophenyl)sulfonyl)-2-(2-(4-methoxyphenyl)hydrazono)-1-phenylethanone (4r). Yield: 62.6 mg (76%); time, 5 h; yellow solid; mp 158−160 °C; TLC, Rf = 0.29 (PE/EtOAc = 9:1). 1 H NMR (CDCl3, 400 MHz): δ 12.43 (s, 1H), 8.20 (s, 2H), 7.77 (d, 2H, J = 6.8 Hz), 7.55−7.35 (m, 4H), 7.23 (d, 1H, J = 8.4 Hz), 7.13 (d, 2H, J = 8.0 Hz), 6.89 (d, 2H, J = 8.0 Hz), 3.78 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 186.5, 166.1 (d, J = 255.4 Hz), 157.6, 137.2, 134.8, 132.1, 131.6 (d, J = 9.7 Hz), 130.1, 127.8, 117.0, 116.3 (d, J = 22.6 Hz), 115.0, 55.6. 19F NMR (CDCl3, 376 MHz): δ −63.17. HRMS (ESI) m/z calcd for C21H18FN2O4S [M + H]+: 413.0965; found, 413.0968. (Z)-2-(2-(4-Methoxyphenyl)hydrazono)-1-phenyl-2-((4(trifluoromethyl)phenyl)sulfonyl)ethanone (4s). Yield: 59.0 mg (64%); time, 10 h; yellow solid; mp 124−126 °C; TLC, Rf = 0.36 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.47 (s, 1H), 8.30 (d, 2H, J = 8.4 Hz), 7.84 (d, 2H, J = 8.4 Hz), 7.77 (d, 2H, J = 7.2 Hz), 7.54 (t, 1H, J = 7.2 Hz), 7.43 (t, 2H, J = 7.2 Hz), 7.15 (d, 2H, J = 8.4 Hz), 6.91 (d, 2H, J = 8.4 Hz), 3.82 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 186.4, 157.8, 144.2, 137.0, 135.3 (q, J = 33.0 Hz), 134.7, 132.2, 130.1, 129.1, 127.9, 127.0 (q, J = 253.4 Hz), 126.1 (q, J = 3.6 Hz), 117.1, 115.0, 55.6. 19F NMR (CDCl3, 376 MHz): δ −63.18. HRMS (ESI) m/z calcd for C22H18F3N2O4S [M + H]+: 463.0934; found, 463.0939. (Z)-2-(2-(4-Methoxyphenyl)hydrazono)-1-phenyl-2-(thiophen-2ylsulfonyl)ethanone (4t). Yield: 45.6 mg (57%); time, 8 h; yellow solid; mp 209−211 °C; TLC, Rf = 0.22 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.2 (s, 1H), 8.06 (dd, 1H, J = 3.6 Hz, J = 1.2 Hz), 7.82 (s, 1H), 7.81 (s, 1H), 7.76 (dd, 1H, J = 4.8 Hz, J = 1.2 Hz), 7.54 (t, 1H, J = 7.2 Hz), 7.43 (t, 2H, J = 7.2 Hz), 7.17 (t, 1H, J = 9.2 Hz), 7.11 (d, 2H, J = 8.0 Hz), 6.89 (d, 2H, J = 8.8 Hz), 3.80 (s, 3H). 13 C NMR (CDCl3, 100 MHz): δ 186.5, 157.6, 137.3, 135.7, 135.2, 134.9, 132.1, 130.1, 127.8, 117.0, 115.0, 55.6. HRMS (ESI) m/z calcd for C19H17N2O4S2[M + H]+: 401.0624; found, 401.0613. (Z)-2-(2-(4-Methoxyphenyl)hydrazono)-2-(naphthalen-2-ylsulfonyl)-1-phenylethanone (4u). Yield: 57.6 mg (65%); time, 8.5 h; yellow solid; mp 181−183 °C; TLC, Rf = 0.33 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.56 (s, 1H), 8.73 (s, 1H), 8.13 (dd, 1H, J = 8.8 Hz, J = 1.6 Hz), 8.03 (q, 2H, J = 8.8 Hz), 7.92 (d, 1H, J = 8.0 Hz), 7.76 (d, 2H, J = 7.2 Hz), 7.68−7.60 (m, 2H), 7.50 (t, 1H, J = 7.2 Hz), 7.39 (t, 2H, J = 8.0 Hz), 7.16 (d, 2H, J = 8.8 Hz), 6.91 (d, 2H, J = 8.8 Hz), 3.82 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 186.5, 157.6, 137.50, 137.36, 135.6, 135.0, 132.1, 132.0, 130.5, 130.1, 130.0, 129.8, 129.4, 129.1, 127.9, 127.7, 127.5, 123.1, 117.0, 115.0, 55.6. HRMS (ESI) m/z calcd for C25H21N2O4S [M + H]+: 445.1216; found, 445.1223. (Z)-2-(Methylsulfonyl)-1-phenyl-2-(2-phenylhydrazono)ethanone (4v). Yield: 38.8 mg (64%); time, 11 h; yellow solid; mp 153−155 °C; TLC, Rf = 0.28 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.28 (s, 1H), 7.90 (d, 2H, J = 8.8 Hz), 7.60 (t, 1H, J = 7.2 Hz), 7.49 (t, 2H, J = 7.2 Hz), 7.37−7.32 (m, 3H), 7.16−7.12 (m, 2H), 3.48 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 187.7, 141.0, 136.9, 132.5, 130.3, 129.7, 128.0, 125.5, 115.6, 45.6. HRMS (ESI) m/ z calcd for C15H15N2O3S [M + H]+: 303.0798; found, 303.0794. (Z)-1-Phenyl-2-(2-phenylhydrazono)-2-tosylethanone (4w). Yield: 53.0 mg (70%); time, 6 h; yellow solid; mp 183−185 °C; TLC, Rf = 0.35 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.43 (s, 1H), 8.05 (d, 2H, J = 6.8 Hz), 7.79 (d, 2H, J = 8.0 Hz), 7.53 (t, 1H, J = 7.2 Hz), 7.43 (d, 2H, J = 6.8 Hz), 7.39−7.33(m, 4H), 7.17 (d, 3H, J = 7.6 Hz), 2.44 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 186.5, 145.4, 141.2, 137.3, 137.1, 132.1, 130.1, 129.66, 129.64, 129.0, 128.6, 127.8, 125.2, 115.5, 21.7. HRMS (ESI) m/z calcd for C21H19N2O3S [M + H]+: 379.1110; found, 379.1118. (Z)-2-(2-(4-Chlorophenyl)hydrazono)-1-phenyl-2-tosylethanone (4x). Yield: 51.0 mg (62%); time, 11 h; yellow solid; mp 187−189 °C; TLC, Rf = 0.38 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.38 (s, 1H), 8.04 (d, 2H, J = 8.0 Hz), 7.76 (d, 2H, J = 8.4 Hz), 7.54 (t, 1H, J = 7.6 Hz), 7.40 (q, 4H, J = 7.6 Hz), 7.32 (d, 2H, J = 8.8 Hz), 7.10 (d, 2H, J = 8.8 Hz), 2.45 (s, 6H). 13C NMR (CDCl3, 100 MHz): δ 186.5, 145.6, 139.9, 137.1, 137.0, 132.3,130.3, 130.1, 129.7, 129.5,

= 249.4 Hz), 157.7, 145.3, 137.1, 134.8, 132.6 (d, J = 8.2 Hz), 130.4 (d, J = 3.1 Hz), 129.6, 128.6, 123.9, 116.9, 115.6, 115.4 (d, J = 22.2 Hz), 55.6, 21.7. 19F NMR (CDCl3, 376 MHz): δ −110.22. HRMS (ESI) m/z calcd for C22H20FN2O4S [M + H]+: 427.1122; found, 427.1105. (Z)-2-(2-(4-Methoxyphenyl)hydrazono)-1-(naphthalen-2-yl)-2tosylethanone (4j). Yield: 61.4 mg (67%); time, 9 h; yellow solid; mp 186−188 °C; TLC, Rf = 0.35 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.49 (s, 1H), 8.37 (s, 1H), 8.08 (d, 2H, J = 8.0 Hz), 7.90−7.84 (m, 4H), 7.62−7.50 (m, 2H), 7.38 (d, 2H, J = 8.0 Hz), 7.14 (d, 2H, J = 8.8 Hz), 6.86 (d, 2H, J = 8.8 Hz), 3.79 (s, 3H), 2.45 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 186.2, 157.4, 145.3, 137.7, 135.1, 135.0, 134.6, 132.3, 131.8, 129.6, 129.3, 128.6, 128.2, 128.1, 127.7, 127.4, 126.6, 126.1, 116.8, 115.0, 55.6, 21.7. HRMS (ESI) m/z calcd for C26H23N2O4S [M + H]+: 459.1373; found, 459.1387. (S,Z)-Methyl-2-benzamido-3-(4-(2-(2-(4-methoxyphenyl)hydrazono)-2-tosylacetyl)phenyl)propanoate (4m). Yield: 77.2 mg (63%); time, 14 h; yellow solid; mp 155−157 °C; TLC, Rf = 0.27 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.43 (s, 1H), 8.03 (d, 2H, J = 8.0 Hz), 7.73−7.69 (m, 4H), 7.50 (t, 1H, J = 7.2 Hz), 7.42−7.34 (m, 4H), 7.17 (d, 2H, J = 8.0 Hz), 7.09 (d, 2H, J = 9.2 Hz), 6.87 (d, 2H, J = 9.2 Hz), 6.63 (d, 1H, J = 7.6 Hz), 3.79 (s, 3H), 3.76 (s, 3H), 3.37−3.29 (m, 2H), 2.43 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 186.1, 171.7, 166.8, 157.5, 145.3, 140.2, 137.5, 136.3, 134.9, 133.6,131.9, 130.3, 129.6, 128.74, 128.67, 128.6, 126.9, 116.8, 115.0, 55.6, 53.4, 52.5, 37.8, 21.7. HRMS (ESI) m/z calcd for C33H32N3O7S [M + H]+: 614.1996; found, 614.2009. (Z)-7-(2-(2-(4-Methoxyphenyl)hydrazono)-2-tosylacetyl)-2Hchromen-2-one (4n). Yield: 80.8 mg (85%); time, 20 h; yellow solid; mp 175−177 °C; TLC, Rf = 0.23 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.58 (s, 1H), 8.05 (d, 2H, J = 8.4 Hz), 7.75− 7.71 (m, 2H), 7.64 (dd, 1H, J = 8.0 and 1.6 Hz), 7.51 (d, 1H, J = 8.0 Hz), 7.38 (d, 2H, J = 8.4 Hz), 7.11 (d, 2H, J = 9.2 Hz), 6.90 (d, 2H, J = 8.4 Hz), 6.51 (d, 1H, J = 9.6 Hz), 3.80 (s, 3H), 2.45 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 184.6, 160.2, 157.8, 153.2, 145.5, 142.6, 140.4, 137.3, 134.6,129.7, 128.6, 128.6, 127.2, 125.7, 121.1, 118.52, 118.47, 117.1, 115.1, 55.6, 21.8. HRMS (ESI) m/z calcd for C25H21N2O6S [M + H]+: 477.1115; found, 477.1091. (Z)-2-(2-(4-Methoxyphenyl)hydrazono)-1-phenyl-2(phenylsulfonyl)ethanone (4o). Yield: 53.6 mg (68%); time, 6 h; yellow solid; mp 195−197 °C; TLC, Rf = 0.34 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.47 (s, 1H), 8.16 (d, 2H, J = 7.6 Hz), 7.7 (d, 2H, J = 6.8 Hz), 7.66 (t, 1H, J = 7.6 Hz), 7.58 (t, 2H, J = 8.0 Hz), 7.52 (t, 1H, J = 7.2 Hz), 7.41 (t, 2H, J = 8.0 Hz), 7.13 (d, 2H, J = 9.2 Hz), 6.90 (d, 2H, J = 8.8 Hz), 3.81 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 186.4, 157.5, 140.6, 137.3, 135.0, 134.0, 132.0, 130.1, 128.9, 128.5, 127.8, 127.7, 116.9, 115.0, 55.6. HRMS (ESI) m/z calcd for C21H19N2O4S [M + H]+: 395.1060; found, 395.1062. (Z)-2-(2-(4-Methoxyphenyl)hydrazono)-2-((4-methoxyphenyl)sulfonyl)-1-phenylethanone (4p). Yield: 59.2 mg (70%); time, 6 h; yellow solid; mp 171−173 °C; TLC, Rf = 0.30 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.42 (s, 1H), 8.11 (d, 2H, J = 8.4 Hz), 7.76 (d, 2H, J = 7.6 Hz), 7.51 (t, 1H, J = 7.2 Hz), 7.41 (t, 2H, J = 7.2 Hz), 7.11(d, 2H, J = 8.8 Hz), 7.03 (d, 2H, J = 8.8 Hz), 6.89 (d, 2H, J = 8.8 Hz), 3.88 (s, 3H), 3.80 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 186.6, 164.1, 157.4, 137.5, 135.0, 131.9, 131.8, 131.1, 130.1, 128.3, 127.7, 55.7, 55.6. HRMS (ESI) m/z calcd for C22H21N2O5S [M + H]+: 425.1165; found, 425.1172. (Z)-2-((4-(tert-Butyl)phenyl)sulfonyl)-2-(2-(4-methoxyphenyl)hydrazono)-1-phenylethanone (4q). Yield: 54.8 mg (61%); time, 6.5 h; yellow solid; mp 147−149 °C; TLC, Rf = 0.24 (PE/EtOAc = 9:1). 1 H NMR (CDCl3, 400 MHz): δ 12.45 (s, 1H), 8.08 (d, 2H, J = 7.2 Hz), 7.78 (d, 2H, J = 8.0 Hz), 7.58 (d, 2H, J = 7.2 Hz), 7.52 (t, 1H, J = 6.8 Hz), 7.41 (t, 2H, J = 7.2 Hz), 7.13 (d, 2H, J = 8.0 Hz), 6.89 (d, 2H, J = 8.0 Hz), 3.81 (s, 3H), 1.34 (s, 9H). 13C NMR (CDCl3, 100 MHz): δ 186.5, 157.9, 157.3, 137.3, 134.9, 131.8, 130.1, 130.0, 128.4, 128.3, 128.0, 127.7, 127.6, 126.0, 125.9, 116.9, 116.7, 55.5, 35.2, 31.0. HRMS (ESI) m/z calcd for C25H27N2O4S [M + H]+: 451.1686; found, 451.1688. 11960

DOI: 10.1021/acs.joc.8b01843 J. Org. Chem. 2018, 83, 11956−11962

Article

The Journal of Organic Chemistry 128.9, 128.7, 127.9, 116.6, 21.8. HRMS (ESI) m/z calcd for C21H18ClN2O3S [M + H]+: 413.0721; found, 413.0726. (Z)-1-Phenyl-2-(2-(o-tolyl)hydrazono)-2-tosylethanone (4y). Yield: 52.6 mg (67%); time, 7.5 h; yellow solid; mp 141−143 °C; TLC, Rf = 0.32 (PE/EtOAc = 9:1). 1H NMR (CDCl3, 400 MHz): δ 12.63 (s, 1H), 8.06 (d, 2H, J = 8.4 Hz), 7.81 (d, 2H, J = 7.2 Hz), 7.56−7.49 (m, 1H), 7.45−7.35 (m, 4H), 7.22(t, 2H, J = 8.4 Hz), 7.17 (t, 1H, J = 7.6 Hz), 7.06 (t, 1H, J = 7.6 Hz), 2.46 (s, 3H), 2.45 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 186.6, 145.4, 139.4, 137.4, 137.2 132.1, 131.1, 130.2, 129.6, 129.4, 128.5, 128.4, 128.1, 127.8, 127.5, 124.9, 124.6, 114.3, 21.7, 16.9. HRMS (ESI) m/z calcd for C22H21N2O3S [M + H]+: 393.1267; found, 393.1269. Synthesis of 3-Sulfonylated Cinnolin-4(1H)-one 5 via BasePromoted Intramolecular Cyclization. To a solution of 4j (0.2 mmol) in 1 mL of EtOH was added 0.5 mL of 0.5 M aqueous sodium carbonate (1.25 eq, 0.25 mmol) dropwise. The resulting mixture was then stirred at reflux for 1 h. After completion of the reaction, EtOH was removed under vacuum, and the residue was extracted by EtOAc (10 mL× 3), dried, concentrated, and purified by column chromatography (eluent: PE/EtOAc = 3:1) to afford 5. Yield: 48.6 mg (60%); time, 1 h; yellow solid; mp 189−191 °C; TLC, Rf = 0.37 (PE/EtOAc = 7:3). 1H NMR (CDCl3, 400 MHz): δ 8.36 (d, 1H, J = 7.6 Hz), 8.15 (d, 2H, J = 8.4 Hz), 7.65 (t, 1H, J = 7.6 Hz), 7.50 (t, 1H, J = 7.6 Hz), 7.43 (d, 2H, J = 8.8 Hz), 7.35 (d, 2H, J = 8.0 Hz), 7.28 (s, 1H), 7.10 (d, 2H, J = 8.8 Hz), 3.93 (s, 3H), 2.43 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ 165.9, 160.6, 144.8, 142.2, 136.4, 134.2, 134.1, 129.5, 129.4, 128.0, 127.3, 127.0, 126.0, 117.9, 115.1, 55.8, 21.7. HRMS (ESI) m/z calcd for C22H19N2O4S [M + H]+: 407.1060; found, 407.1063.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.8b01843. Crystal structure of 4d and the corresponding data and copies of 1H and 13C NMR spectra (PDF) X-ray crystallography data of 4d (CIF)

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AUTHOR INFORMATION

Corresponding Authors

*(W.-C.G.) E-mail: [email protected]. *(R.Z.) E-mail: [email protected]. ORCID

Wen-Chao Gao: 0000-0002-1382-6210 Rong Zhou: 0000-0002-0322-9199 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (No. 21502135) and Natural Science Foundation of Shanxi Province (No. 2015021037).

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REFERENCES

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DOI: 10.1021/acs.joc.8b01843 J. Org. Chem. 2018, 83, 11956−11962

Article

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DOI: 10.1021/acs.joc.8b01843 J. Org. Chem. 2018, 83, 11956−11962