Palladium-Catalyzed Oxidative Cross-Coupling of Arylhydrazines and

zines and Arenethiols with Molecular Oxygen as the Sole Oxidant. **. Changliu Wang, Zhenming Zhang, Yongliang Tu, Ying Li, Jiale Wu, Junfeng Zhao**...
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Cite This: J. Org. Chem. 2018, 83, 2389−2394

Palladium-Catalyzed Oxidative Cross-Coupling of Arylhydrazines and Arenethiols with Molecular Oxygen as the Sole Oxidant Changliu Wang, Zhenming Zhang, Yongliang Tu, Ying Li, Jiale Wu, and Junfeng Zhao* Key Laboratory of Chemical Biology of Jiangxi Province, College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, P. R. China S Supporting Information *

ABSTRACT: A highly efficient palladium-catalyzed oxidative cross-coupling of arylhydrazines and arenethiols with molecular oxygen as the sole oxidant to afford unsymmetrical diaryl sulfides has been developed. The only byproducts are nitrogen and water. A broad range of functional groups, even the reactive iodides, are tolerated and thus offer the opportunity for further functionalization.

T

Scheme 1. Synthetic Strategies for Diaryl Sulfides via Palladium-Catalyzed Cross-Coupling of Arenethiols

ransition metal-catalyzed oxidative cross-coupling reactions have emerged as powerful and general tools for carbon-carbon and carbon-heteroatom bond formation over the past decade.1 However, among these reactions, the formation of a carbon−sulfur bond via oxidative cross-coupling of thiols has attracted less attention2 due to the homocoupling of thiols under the oxidative reaction conditions.3 In addition, diaryl sulfides are of great importance as building block in biologically active molecules,4 pharmaceuticals,5 and natural products.6 As a consequence, their syntheses have attracted considerable attention.7 Recently, transition metal-catalyzed traditional cross-coupling reactions have been developed to construct a sp2 C−S bond.8 Although significant advances have been made along these lines, the development of efficient synthetic methodologies for diaryl sulfides via palladium-catalyzed oxidative cross-coupling still remains a challenging topic. The palladium-catalyzed cross-coupling reaction of arenethiols with different electrophiles represents one of the most straightforward tools to afford a variety of unsymmetrical diaryl sulfides (Scheme 1, eq 1).9 These classic methods for carbonsulfur bond formation involve an addition−elimination mechanism by using Pd(0) as catalyst. However, these methods are usually limited in substrate scope and require harsh reaction conditions.10 Compared with Pd(0)-catalyzed reactions carried out under inert atmosphere, Pd(II)-catalyzed coupling reactions are relatively easy to handle.11 Recently, the Pd(II)catalyzed decarboxylative cross-coupling reaction of benzoic acids with arenethiols or disulfides using Ag or Cu salts as oxidant to afford diaryl sulfide derivatives has been reported (Scheme 1, eq 2).12 Herein, we disclosed a novel and efficient Pd(II)-catalyzed oxidative cross-coupling reaction of arylhydrazines with arenethiols using O2 as the sole oxidant to give unsymmetrical diaryl sulfides (Scheme 1, eq 3). Arylhydrazines have evolved into environmentally friendly arylation agents for palladium-catalyzed oxidative crosscoupling reactions because the only byproducts are water and nitrogen.13 Our group is interested in C−N bond cleavage of arylhydrazines and reported the palladium-catalyzed oxidative © 2018 American Chemical Society

carbonylation of arylhydrazines with alkynes, phenols, and amines.14 On the basis of these works, we envisioned that arenethiols could also react with arylhydrazines to afford the corresponding diaryl sulfides through palladium-catalyzed oxidative cross-coupling. With this proposal in mind, we started by testing different palladium catalysts in the oxidative crosscoupling of phenylhydrazine hydrochloride 1a and 4-methoxybenzenethiol 2a with 10 mol % of PPh3, 2 equiv of Na2CO3 in dimethyl sulfoxide (DMSO) at 100 °C for 12 h under balloon pressure of O2 (Table 1). Preliminary screening revealed that Pd(OAc)2 was most effective for this transformation (Table 1, entries 1−6). Further exploration of ligands disclosed that the ligand is crucial and that PCy3 gave the best yield (Table 1, entries 7−12). The base also played an important role in this reaction, and Na2CO3 was identified to be the best one among others (Table 1, entries 13−17). In addition, toluene demonstrated a beneficial effect on this reaction (Table 1, Received: November 18, 2017 Published: January 16, 2018 2389

DOI: 10.1021/acs.joc.7b02926 J. Org. Chem. 2018, 83, 2389−2394

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The Journal of Organic Chemistry Table 1. Optimization of the Reaction Conditionsa

Scheme 2. Substrate Scope of Arylhydrazinesa

entry

catalyst

ligand

base

solvent

yield (%)b

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21c 22d 23e

PdCl2(PPh3)2 PdCl2(dppf) Pd(PPh3)4 Pd2(dba)3 Pd(TFA)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2 Pd(OAc)2

PPh3 PPh3 PPh3 PPh3 PPh3 PPh3 P(o-Tol)3 PCy3 P(2-furyl)3 Binap 1,10-Phen

Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Cs2CO3 K2CO3 NaOH Et3N DBU Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3

DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO PhMe DMF PhCF3 PhMe PhMe PhMe

52 51 58 43 53 70 27 77 47 53 64 trace 73 75 27 38 30 82 46 67 60 25 trace

PCy3 PCy3 PCy3 PCy3 PCy3 PCy3 PCy3 PCy3 PCy3 PCy3 PCy3

a Reaction conditions: 1 (0.4 mmol), 2a (0.2 mmol), Pd(OAc)2 (5 mol %), PCy3 (10 mol %), Na2CO3 (0.4 mmol), PhMe (2.0 mL) under an O2 balloon at 100 °C for 12 h.

Scheme 3. Substrate Scope of Arenethiolsa

a Reaction conditions: 1a (0.4 mmol), 2a (0.2 mmol), base (0.4 mmol), Pd catalyst (5 mol %), ligand (10 mol %), solvent (2.0 mL) at 100 °C for 12 h with an O2 balloon. bIsolated yield. cAt 60 °C. dUnder air. eUnder N2.

entries 18−20). Decreasing the reaction temperature has a deleterious effect on the reaction efficiency (Table 1, entry 21). As expected, there is no reaction at all when the experiment was performed under a N2 atmosphere (Table 1, entry 23). With the optimized reaction conditions in hand (Table 1, entry 18), we explored the scope of this oxidative crosscoupling reaction between various arylhydrazines and 4methoxybenzenethiol. As shown in Scheme 2, a broad range of arylhydrazines with ortho-, meta-, or para-alkyl substituents reacted equally well with 4-methoxybenzenethiol 2a to afford the corresponding products (3ba−3fa) in 77−84% yields. Even the sterically demanding dimethyl substituents were tolerated to furnish the desired products (3ga and 3ha) in high yields. It should be noted that the reaction could be conducted in the presence of halogen substituents (3ia−3la) and that the carbon−halogen bonds, which are reactive under conventional palladium-catalyzed cross-coupling conditions, were intact. Moreover, diaryl sulfides containing a strong electron-withdrawing (3na) substituent could also be prepared using this method. In addition, (4-(trifluoromethoxy)phenyl)hydrazine and naphthalen-2-ylhydrazine could afford the coupling products (3ma and 3oa) in high yields. Disappointingly, no target products were obtained when heterocyclic hydrazines were used. Next, the palladium-catalyzed oxidative cross-coupling reactions of (4-nitrophenyl)hydrazine hydrochloride (1n) with a variety of arenethiols were also examined, and the results are summarized in Scheme 3. Arenethiols with a series

a

Reaction conditions: 1n (0.4 mmol), 2 (0.2 mmol), Pd(OAc)2 (5 mol %), PCy3 (10 mol %), Na2CO3 (0.4 mmol), PhMe (2.0 mL) under an O2 balloon at 100 °C for 12 h.

of electron-donating groups, such as 4-methyl, 4-ethyl, 4-tbutyl, 3-methoxy, and 3,5-dimethyl, could convert to the corresponding products (3nc−3ng) in good to high yields. Interestingly, the halogen substituents such as -Cl and -Br could be tolerated in this reaction and afforded the diaryl sulfide products (3nh and 3ni) in 79 and 83% yields, respectively, and thus offering an advantage for further manipulation by conventional coupling reaction. Then, 4-(trifluoromethoxy)benzenethiol and naphthalene-1-thiol were also converted to the coupling products (3nj and 3nk) in good yields. However, no reaction occurred when 4-nitrobenzenethiol (3nl) was employed as substrate. 2390

DOI: 10.1021/acs.joc.7b02926 J. Org. Chem. 2018, 83, 2389−2394

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The Journal of Organic Chemistry The potential application of this oxidative cross-coupling reaction is illustrated in Scheme 4. Diaryl sulfide 3ka could be

Scheme 6. Proposed Reaction Mechanism

Scheme 4. Synthetic Application

intermediate B. Then, the active palladium species C might be formed through transmetalation of species A with intermediate B. Finally, reductive elimination afforded the coupling product D and regenerated the Pd catalyst to close the catalytic cycle.

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CONCLUSIONS In summary, we have developed the first palladium-catalyzed oxidative cross-coupling of arylhydrazines and arenethiols with O2 as the sole oxidant to afford diaryl sulfides in good to high yields. A variety of functional groups including halide substituents, which are reactive under conventional transition metal-catalyzed cross-coupling reaction conditions, are tolerated. This method provides a highly efficient approach to unsymmetrical diaryl sulfides.

prepared efficiently from the palladium-catalyzed crosscoupling of 1k and 2a (Scheme 4, path a). Interestingly, the cross-coupling of 2l and 1p could also offer the same diaryl sulfide 3ka in good yield (Scheme 4, path b). Such a feature will be remarkably useful when one coupling partner is expensive or not available. Furthermore, product 3ka could efficiently undergo Hiyama and Suzuki reactions to afford the corresponding coupling product 6a in 77 and 85% yields, respectively (Scheme 4, paths c and d). To probe whether a transition metal-free radical pathway was involved in this reaction mechanism,15 we performed several experiments as shown in Scheme 5. When 1a was treated with

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EXPERIMENTAL SECTION

All reactions were carried out in oven-dried glassware. All arylhydrazine hydrochloride and arenethiols were obtained from commercial sources and used without further purification. All the reactions were monitored by thin-layer chromatography (TLC); products were purified by using silica gel column chromatography. 1 H/13C NMR spectra were recorded on a Bruker Avance 400 MHz and Bruker AMX 400 MHz spectrometer at 400/100 MHz, respectively, in CDCl3 unless otherwise stated using either TMS or the undeuterated solvent residual signal as the reference. Chemical shifts are given in ppm and are measured relative to CDCl3 as an internal standard. Mass spectra were obtained by electrospray ionization time-of-flight (ESI-TOF) mass spectrometry. Flash column chromatography purification of compounds was carried out by gradient elution using ethyl acetate (EA) in light petroleum ether (PE). General Procedure for the Preparation of Unsymmetrical Diaryl Sulfides. Arenethiol (0.2 mmol, 1.0 equiv), arylhydrazine hydrochloride (0.4 mmol, 2.0 equiv), Pd(OAc)2 (1.1 mg, 0.01 mmol, 5 mol %), PCy3 (5.6 mg, 0.02 mmol 10 mol %), and Na2CO3 (42.4 mg, 0.4 mmol, 2.0 equiv) were combined in an oven-dried Schlenk tube equipped with a stir bar. After the addition of all of the solid reagent, the balloon filled with O2 was connected to the Schlenk tube via a syringe. The Schlenk tube was heated at 100 °C for 12 h. After the reaction was completed (monitored by TLC), the contents were cooled to room temperature, and then the balloon gas was released. The solvent was removed under reduced pressure to give crude products, which were purified by column chromatography (inner diameter: 3.0 cm and length: 30 cm) over silica gel (PE/EA) to afford pure products. (4-Methoxyphenyl)(phenyl)sulfane (3aa).16 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3aa as a pale yellow oil (35.4 mg, 82%); Rf = 0.40 (PE/EA = 50:1, v/v); IR (KBr) ν̃ 2945, 2834, 1588, 1487, 1245, 1023, 826 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 8.8 Hz, 2H), 7.31−7.01 (m, 5H), 6.89 (d, J = 8.8

Scheme 5. Control Experiments

2a in the absence of Pd catalyst, only a small amount of desired product 3aa was obtained (Scheme 5, eq 1). A significantly lower yield of 3aa was observed when disulfide 4a was used under the standard conditions (Scheme 5, eq 2). Furthermore, the control experiment with 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) demonstrated that the reaction efficiency was kept intact in the presence of the radical scavenger (Scheme 5, eq 3). All of these experiments indicate that a radical pathway was not likely to be involved in this reaction. A possible reaction mechanism for the palladium-catalyzed oxidative cross-coupling reaction of arylhydrazines with arenethiols was proposed in Scheme 6. Aryl palladium species A was initially produced by the oxidative C−N bond cleavage of arylhydrazine with Pd(OAc)2 under O2.13a On the other hand, arenethiol reacted with base to yield the benzenethiolate 2391

DOI: 10.1021/acs.joc.7b02926 J. Org. Chem. 2018, 83, 2389−2394

Note

The Journal of Organic Chemistry Hz, 2H), 3.80 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 159.9, 138.6, 135.3, 128.9, 128.3, 125.8, 124.4, 115.0, 55.4. (4-Methoxyphenyl)(p-tolyl)sulfane (3ba).17 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3ba as a colorless oil (35.4 mg, 77%); Rf = 0.60 (PE/EA = 50:1, v/v); IR (KBr) ν̃ 2936, 2839, 1593, 1497, 1244, 1032, 826 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.46−7.29 (m, 2H), 7.23−7.14 (m, 1H), 7.14−7.03 (m, 2H), 7.00 (d, J = 7.6, 1H), 6.95−6.82 (m, 2H), 3.82 (s, 3H), 2.40 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 159.6, 137.2, 137.0, 134.5, 130.2, 129.2, 126.5, 126.2, 124.0, 115.01, 55.4, 20.3. (4-Methoxyphenyl)(m-tolyl)sulfane (3ca).17 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3ca as a colorless oil (38.7 mg, 79%); Rf = 0.45 (PE/EA = 50:1, v/v); IR (KBr) ν̃ 2925, 2834, 1588, 1497, 1250, 1028, 826 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.48−7.34 (m, 2H), 7.13 (t, J = 7.7 Hz, 1H), 7.03 (s, 1H), 6.97 (t, J = 6.7 Hz, 2H), 6.92−6.85 (m, 2H), 3.83 (s, 3H), 2.28 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 159.8, 138.8, 138.2, 135.1, 129.1, 128.8, 126.8, 125.6, 124.7, 115.0, 55.4, 21.3. (4-Methoxyphenyl)(o-tolyl)sulfane (3da).16 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3da as a colorless oil (41.2 mg, 84%); Rf = 0.50 (PE/EA = 50:1, v/v); IR (KBr) ν̃ 3011, 2920, 1593, 1492, 1244, 1028, 805 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.36 (d, J = 8.9 Hz, 2H), 7.14 (d, J = 8.2 Hz, 2H), 7.07 (d, J = 8.1 Hz, 2H), 6.87 (d, J = 8.8 Hz, 2H), 3.81 (s, 3H), 2.31 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 159.5, 136.2, 134.3, 134.3, 129.8, 129.4, 125.7, 114.9, 55.4, 21.0. (4-Ethylphenyl)(4-methoxyphenyl)sulfane (3ea). Purification by chromatography (PE/EA = 100:1, v/v) afforded 3ea as a colorless oil (41.2 mg, 84%); Rf = 0.60 (PE/EA = 50:1, v/v); IR (KBr) ν̃ 2965, 2839, 1593, 1492, 1245, 1032, 832 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.36 (d, J = 8.8 Hz, 2H), 7.14 (d, J = 8.3 Hz, 2H), 7.08 (d, J = 8.2 Hz, 2H), 6.86 (d, J = 8.8 Hz, 2H), 3.79 (s, 3H), 2.59 (q, J = 7.6 Hz, 2H), 1.20 (t, J = 7.6 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 159.5, 142.5, 134.7, 134.5, 129.3, 128.6, 125.6, 114.9, 55.4, 28.4, 15.5. HRMS (ESI-TOF) calcd for C15H17OS [M + H]+: 245.0995; found: 245.0992 (4-(tert-Butyl)phenyl)(4-methoxyphenyl)sulfane (3fa).17 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3fa as a colorless oil (44.6 mg, 82%); Rf = 0.60 (PE/EA = 50:1, v/v); IR (KBr) ν̃ 2965, 2899, 1593, 1492, 1250, 1032, 821 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.39 (d, J = 8.9 Hz, 2H), 7.26 (d, J = 8.6 Hz, 2H), 7.13 (d, J = 8.6 Hz, 2H), 6.87 (d, J = 8.9 Hz, 2H), 3.80 (s, 3H), 1.28 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 159.6, 149.2, 134.8, 134.7, 128.6, 126.0, 125.2, 114.9, 55.4, 34.4, 31.3. (3,4-Dimethylphenyl)(4-methoxyphenyl)sulfane (3ga). Purification by chromatography (PE/EA = 100:1, v/v) afforded 3ga as a colorless oil (39.1 mg, 80%); Rf = 0.45 (PE/EA = 50:1, v/v); IR (KBr) ν̃ 2940, 2834, 1587, 1497, 1239, 1033, 826 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.37 (d, J = 8.8 Hz, 2H), 7.16−6.94 (m, 3H), 6.88 (d, J = 8.8 Hz, 2H), 3.82 (s, 3H), 2.23 (s, 3H), 2.21 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 159.4, 137.4, 135.0, 134.4, 134.2, 130.8, 130.3, 127.1, 126.0, 114.9, 55.4, 19.7, 19.3; HRMS (ESI-TOF) calcd for C15H17OS [M + H]+: 245.0995; found: 245.0992. (3,5-Dimethylphenyl)(4-methoxyphenyl)sulfane (3ha).17 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3ha as a colorless oil (37.6 mg, 77%); Rf = 0.50 (PE/EA = 50:1, v/v); IR (KBr) ν̃ 2925, 2834, 1593, 1497, 1250, 1038, 832 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.52−7.32 (m, 2H), 6.97−6.87 (m, 2H), 6.84 (s, 2H), 6.81 (d, J = 0.5 Hz, 1H), 3.83 (s, 3H), 2.25 (s, 6H); 13C NMR (100 MHz, CDCl3) δ 159.7, 138.6, 137.8, 135.0, 127.9, 126.3, 124.9, 114.9, 55.4, 21.2. (4-Fluorophenyl)(4-methoxyphenyl)sulfane (3ia).17 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3ia as a colorless oil (33.2 mg, 71%); Rf = 0.60 (PE/EA = 50:1, v/v); IR (KBr) ν̃ 2940, 2834, 1588, 1493, 1420, 1033, 826; 1H NMR (400 MHz, CDCl3) δ 7.35 (d, J = 8.8 Hz, 2H), 7.23−7.16 (m, 2H), 6.99−6.91 (m, 2H), 6.87 (d, J = 8.8 Hz, 2H), 3.80 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 161.6 (d, JCF = 245.9 Hz), 159.7, 134.5, 133.1 (d, JCF = 3.3 Hz), 131.1 (d, JCF = 8.0 Hz), 125.3, 116.1 (d, JCF = 22.0 Hz), 115.0, 55.4.

(4-Chlorophenyl)(4-methoxyphenyl)sulfane (3ja).17 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3ja as a colorless oil (37.0 mg, 74%); Rf = 0.60 (PE/EA = 50:1, v/v); IR (KBr) ν̃ 3096, 2965, 1593, 1502, 1330, 1083, 851 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.40 (d, J = 8.8 Hz, 2H), 7.19 (d, J = 8.7 Hz, 2H), 7.08 (d, J = 8.7 Hz, 2H), 6.91 (d, J = 8.8 Hz, 2H), 3.83 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 160.1, 137.4, 135.5, 131.7, 129.4, 129.0, 123.9, 115.2, 55.4. (4-Bromophenyl)(4-methoxyphenyl)sulfane (3ka).17 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3ka as a yellow oil (43.6 mg, 74%); Rf = 0.55 (PE/EA = 50:1, v/v); IR (KBr) ν̃ 3091, 2960, 1593, 1502, 1335, 1084, 851 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 8.8 Hz, 2H), 7.33 (d, J = 8.6 Hz, 2H), 7.01 (d, J = 8.6 Hz, 2H), 6.91 (d, J = 8.8 Hz, 2H), 3.83 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 160.1, 138.2, 135.6, 131.9, 129.5, 123.6, 119.4, 115.2, 55.4. (4-Iodophenyl)(4-methoxyphenyl)sulfane (3la).18 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3la as a colorless oil (56.3 mg, 77%); Rf = 0.60 (PE/EA = 50:1, v/v); IR (KBr) ν̃ 2936, 2830, 1593, 1492, 1250, 1033, 852 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 8.5 Hz, 2H), 7.41 (d, J = 8.8 Hz, 2H), 6.89 (dd, J1 = 14.7, J2 = 8.7 Hz, 4H), 3.83 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 160.2, 139.2, 137.8, 135.8, 129.6, 123.3, 115.2, 90.2, 55.4. (4-Methoxyphenyl)(4-(trifluoromethoxy)phenyl)sulfane (3ma).17 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3ma as a colorless oil (48.0 mg, 80%); Rf = 0.60 (PE/EA = 50:1, v/v); IR (KBr) ν̃ 2940, 2834, 1588, 1493, 1255, 1033, 832; 1H NMR (400 MHz, CDCl3) δ 7.42 (d, J = 8.8 Hz, 2H), 7.18−7.10 (m, 2H), 7.11− 7.00 (m, 2H), 6.91 (d, J = 8.8 Hz, 2H), 3.82 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 160.2, 147.2, 137.7, 135.7, 129.1, 123.6, 121.5 (JCF = 256.0), 119.2, 115.2, 55.4. (4-Methoxyphenyl)(4-nitrophenyl)sulfane (3na).17 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3na as a yellow solid (39.2 mg, 74%); Rf = 0.60 (PE/EA = 50:1, v/v); mp 62−63 °C; IR (KBr) ν̃ 2930, 2834, 1593, 1497, 1240, 1023, 751 cm−1; 1H NMR (400 MHz, CDCl3) δ 8.03 (d, J = 9.0 Hz, 2H), 7.48 (d, J = 8.8 Hz, 2H), 7.09 (d, J = 9.0 Hz, 2H), 6.99 (d, J = 8.8 Hz, 2H), 3.86 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ 161.1, 150.0, 145.1, 137.1, 125.6, 124.0, 120.2, 115.7, 55.5. (4-Methoxyphenyl)(naphthalen-2-yl)sulfane (3oa).17 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3oa as a white solid (41.9 mg, 80%); Rf = 0.40 (PE/EA = 50:1, v/v); mp 67−69 °C; IR (KBr) ν̃ 2930, 2834, 1593, 1493, 1239, 1023, 826 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.80−7.74 (m, 1H), 7.74−7.64 (m, 2H), 7.61 (d, J = 1.3 Hz, 1H), 7.51−7.37 (m, 4H), 7.31−7.30 (m, 1H), 6.99− 6.88 (m, 2H), 3.84 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 159.9, 135.9, 135.2, 133.8, 131.8, 128.5, 127.7, 127.2, 126.8, 126.5, 126.5, 125.6, 124.5, 115.1, 55.4. (4-Nitrophenyl)(phenyl)sulfane (3nb).16 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3nb as a yellow solid (37.9 mg, 82%); mp 55−56 °C; Rf = 0.40 (PE/EA = 50:1, v/v); IR (KBr) ν̃ 3057, 2925, 1568, 1512, 1336, 1078, 847 cm−1; 1H NMR (400 MHz, CDCl3) δ 8.06 (d, J = 9.0 Hz, 2H), 7.55−7.53 (m, 2H), 7.46−7.45 (m, 3H), 7.18 (d, J = 9.0 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 148.5, 145.4, 134.7, 130.6, 130.0, 129.7, 126.8, 124.0. 4-Nitrophenyl)(p-tolyl)sulfane (3nc).16 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3nc as a yellow solid (40.2 mg, 82%); Rf = 0.50 (PE/EA = 50:1, v/v); mp 79−81 °C; IR (KBr) ν̃ 3445, 2920, 1578, 1508, 1341, 1084, 806 cm−1; 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 9.0 Hz, 2H), 7.43 (d, J = 8.1 Hz, 2H), 7.26 (d, J = 7.7 Hz, 2H), 7.13 (d, J = 9.0 Hz, 2H), 2.41 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 149.3, 145.2, 140.2, 135.1, 130.9, 126.6, 126.2, 124.0, 21.3. (4-Ethylphenyl)(4-nitrophenyl)sulfane (3nd).18 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3nd as a yellow solid (41.4 mg, 80%); Rf = 0.40 (PE/EA = 50:1, v/v); mp 87−88 °C; IR (KBr) ν̃ 3090, 2950, 1580, 1505, 1351, 1077, 850 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 9.0 Hz, 2H), 7.38 (d, J = 8.2 Hz, 2H), 7.21 (d, J = 8.3 Hz, 2H), 7.06 (d, J = 9.1 Hz, 2H), 2.63 (q, J = 7.6 2392

DOI: 10.1021/acs.joc.7b02926 J. Org. Chem. 2018, 83, 2389−2394

The Journal of Organic Chemistry

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Hz, 2H), 1.20 (t, J = 7.6 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 148.3, 145.4, 144.2, 134.1, 128.6, 125.8, 125.2, 123.0, 27.6, 14.2. (4-(tert-Butyl)phenyl)(4-nitrophenyl)sulfane (3ne).16 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3ne as a colorless solid (43.1 mg, 75%); Rf = 0.40 (PE/EA = 50:1, v/v); mp 65−66 °C; IR (KBr) ν̃ 3097, 2945, 1578, 1508, 1331, 1078, 841 cm−1; 1H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 8.9 Hz, 2H), 7.47 (s, 4H), 7.16 (d, J = 9.0 Hz, 2H), 1.36 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 153.3, 149.1, 145.2, 134.7, 127.1, 126.7, 126.4, 124.0, 34.9, 31.2. (3-Methoxyphenyl)(4-nitrophenyl)sulfane (3nf).16 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3nf as a yellow solid (43.3 mg, 83%); Rf = 0.45 (PE/EA = 50:1, v/v); mp 78−80 °C; IR (KBr) ν̃ 3445, 2961, 1583, 1502, 1331, 1078, 857 cm−1; 1H NMR (400 MHz, CDCl3) δ 8.07 (d, J = 9.0 Hz, 2H), 7.36 (t, J = 8.0 Hz, 1H), 7.21 (d, J = 9.0 Hz, 2H), 7.12 (d, J = 7.7 Hz, 1H), 7.09−7.04 (m, 1H), 7.02−6.93 (m, 1H), 3.82 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 160.6, 148.2, 145.5, 131.6, 130.8, 126.9, 126.7, 124.1, 119.6, 115.6, 55.5. (3,5-Dimethylphenyl)(4-nitrophenyl)sulfane (3 ng).19 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3 ng as a yellow solid (39.9 mg, 77%); Rf = 0.5 (PE/EA = 50:1, v/v); mp 98−100 °C; IR (KBr) ν̃ 2930, 2829, 1593, 1493, 1245, 1028, 745 cm−1; 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 9.0 Hz, 2H), 7.17 (s, 1H), 7.15 (d, J = 2.1 Hz, 3H), 7.08 (s, 1H), 2.34 (s, 6H); 13C NMR (100 MHz, CDCl3) δ 149.1, 145.3, 139.8, 132.4, 131.5, 129.7, 126.6, 124.0, 21.2. (4-Chlorophenyl)(3-nitrophenyl)sulfane (3nh).20 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3nh as a yellow solid (41.9 mg, 79%); Rf = 0.40 (PE/EA = 50:1, v/v); mp 87−88 °C; IR (KBr) ν̃ 2930, 2830, 1588, 1487, 1245, 1028, 741 cm−1; 1H NMR (400 MHz, CDCl3) δ 8.08 (d, J = 8.8 Hz, 2H), 7.47 (d, J = 8.5 Hz, 2H), 7.42 (d, J = 8.6 Hz, 2H), 7.19 (d, J = 8.9 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 147.5, 145.7, 136.1, 135.8, 130.3, 129.3, 127.1, 124.2. (4-Bromophenyl)(3-nitrophenyl)sulfane (3ni).20 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3ni as a yellow solid (51.1 mg, 83%); Rf = 0.45 (PE/EA = 50:1, v/v); mp 92−93 °C; IR (KBr) ν̃ 3097, 2945, 1578, 1508, 1331, 1078, 841 cm−1; 1H NMR (400 MHz, CDCl3) δ 8.08 (d, J = 8.7 Hz, 2H), 7.58 (d, J = 8.3 Hz, 2H), 7.39 (d, J = 8.3 Hz, 2H), 7.20 (d, J = 8.7 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 147.3, 145.7, 135.9, 133.2, 132.5, 130.0, 127.2, 124.2. (4-Nitrophenyl)(4-(trifluoromethoxy)phenyl)sulfane (3nj).17 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3nj as a yellow solid (50.8 mg, 80%); Rf = 0.40 (PE/EA = 50:1, v/v); mp 84− 86 °C; IR (KBr) ν̃ 2940, 2834, 1588, 1493, 1255, 1033, 832; 1H NMR (400 MHz, CDCl3) δ 8.02 (d, J = 7.6 Hz, 2H), 7.49 (d, J = 7.3 Hz, 2H), 7.22 (d, J = 7.9 Hz, 2H), 7.14 (d, J = 7.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 150.1, 147.2, 145.8, 136.0, 129.4, 127.2, 124.2, 122.2, 120.4 (JCF = 257.0). Naphthalen-1-yl(4-nitrophenyl)sulfane (3nk).21 Purification by chromatography (PE/EA = 100:1, v/v) afforded 3nk as a red solid (40.5 mg, 72%); Rf = 0.40 (PE/EA = 50:1, v/v); mp 84−86 °C; IR (KBr) ν̃ 3445, 3091, 1572, 1497, 1331, 1084, 766 cm−1; 1H NMR (400 MHz, CDCl3) δ 8.13 (d, J = 8.0 Hz, 1H), 7.93−7.75 (m, 5H), 7.42 (d, J = 7.4, 3H), 6.98−6.81 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 148.5, 145.2, 135.8, 134.6, 134.2, 131.5, 129.0, 127.8, 127.0, 126.8, 126.1, 126.0, 125.5, 124.0. [1,1′-Biphenyl]-4-yl(4-methoxyphenyl)sulfane (6a).22 Purification by chromatography (PE/EA = 100:1, v/v) afforded 6a as a white solid (40.5 mg, 72%); Rf = 0.30 (PE/EA = 50:1, v/v); mp 137−138 °C; 1H NMR (400 MHz, CDCl3) δ 7.45 (d, J = 7.2 Hz, 2H), 7.37 (dd, J1 = 8.6, J2 = 4.0 Hz, 4H), 7.32 (t, J = 7.6 Hz, 2H), 7.23−7.25 (m, 1H), 7.14 (d, J = 8.5 Hz, 2H), 6.83 (d, J = 8.8 Hz, 2H), 3.73 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 158.9, 139.4, 137.7, 136.7, 134.4, 127.8, 127.5, 126.6, 126.2, 125.8, 123.16, 114.0, 54.4.

Note

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.7b02926. Copies of 1H and 13NMR spectra for all compounds (PDF)

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Junfeng Zhao: 0000-0003-4843-4871 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 (21462023, 21762021) and the Natural Science Foundation of Jiangxi Province (20143ACB20007, 20153BCB23018, and 20161BAB213069).

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REFERENCES

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