Nitration and Cyclization of Arene-Alkynes: An Access to 9

Nitration and Cyclization of Arene-Alkynes: An Access to 9-Nitrophenathrenes. Wangsheng Liu,† Yanbin Zhang,† and Hao Guo*,†,‡. † Department ...
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Cite This: J. Org. Chem. 2018, 83, 10518−10524

Nitration and Cyclization of Arene-Alkynes: An Access to 9‑Nitrophenathrenes Wangsheng Liu,† Yanbin Zhang,† and Hao Guo*,†,‡ †

Department of Chemistry, Fudan University, 2005 Songhu Road, Shanghai, 200438, P. R. China Academy for Engineering and Technology, Fudan University, 220 Handan Road, Shanghai, 200433, P. R. China

‡

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ABSTRACT: A nitration and cyclization of arene-alkynes has been developed, affording 9-nitrophenathrenes efficiently. This reaction probably proceeds via addition of the nitrogen dioxide to the alkyne moiety, intramolecular radical addition of vinyl radical to one aryl ring, oxidation of radical intermediate into carbocation species, and elimination of a proton. In this transformation, Fe(NO3)3 was used as both nitro source and oxidant.

N

Scheme 2. Nitration of Alkynes

itroolefins are a prominent class of molecules existing widely in agrochemicals,1 pharmaceuticals,2 and natural products.3 In organic synthesis, nitroolefins are also ubiquitous building blocks.4 One of the most representative synthetic methods to obtain nitroolefins is based on the addition of nitrogen dioxide to alkene after which elimination of a hydrogen/ proton from the resulting alkyl radical intermediate gives the nitroolefin product5 (Scheme 1). However, methods for conScheme 1. Nitration of Alkenes

structing nitroalkenes via 2-nitrovinyl species generated from the addition of nitrogen dioxides to alkynes are rare because 2-nitrovinyl intermediate is highly unstable and has high reactivity and a short lifetime.6 Normally, there are two main ways to realize such a transformation. One is the intermolecular radical trapping reaction, which remained undeveloped until the past decade.6,7 In this way, 2-nitrovinyl radicals can be captured by iodine or TEMPO, forming polysubstituted nitroolefins (Scheme 2a). The other is the intramolecular radical trapping reaction in which 2-nitrovinyl radicals first undergo a radical cyclization when an unsaturated bond is incorporated at an appropriate position.8 In this way, the resulting alkyl radical intermediate will be further oxidized by TEMPO to enable the elimination of a proton to afford the final products (Scheme 2b). Direct accesses to phenanthrene derivatives or 1,2-dihydronaphthalene derivatives from 4-arylalkynes have been wellstudied.9 Various functional groups, such as halogen,10 sulfide,11 selenium,12 tellurium,12 sulfone,13 and trifluoromethyl14 can be introduced into the final products (Scheme 3). In most cases of such a transformation, the first step is undertaken via the © 2018 American Chemical Society

Scheme 3. Cyclization and Functionalization of 4-Arylalkynes

addition of the positive ion into the alkyne moiety.10−12 Only trifluoromethylation and sulfone reactions proceed via a radical addition-initiated procedure.13,14 Obviously, radical additioninitiated reactions in this field are less studied. To the best of our knowledge, nitration and cyclization of 4-arylalkynes affording 9-nitrophenanthrene derivatives has not been Received: May 11, 2018 Published: August 3, 2018 10518

DOI: 10.1021/acs.joc.8b01201 J. Org. Chem. 2018, 83, 10518−10524

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The Journal of Organic Chemistry

With optimized reaction conditions in hand, we started to investigate the scope of this reaction (Table 2). A series of mono-, di-, or trisubstituted arene-alkynes were tested under condition A. We first studied the electronic effect of monosubstituted arene-alkynes. With strong electron-donating groups, like methoxy and acetoxy, the reaction was completed in a short time, generating the desired products (2a and 2b) in good yields. Weak electron-donating group, like t-butyl and phenyl, substituted reactants also gave the corresponding products (2c and 2d) in moderate yields. When substrates with weak electron-withdrawing group, like chlorine, were tested, higher temperature was required to complete the transformation (2f and 2g). Reactions for substrates bearing strong electron-withdrawing groups, such as nitro and cyano, gave similar results (2h and 2i). Finally, some di- or trisubstituted substrates were applied under condition A, and multisubstituted nitrophenathrenes were formed in good yields (2j−l). Further studies indicated that this reaction also worked with heteroaromatic substituents in the alkyne moiety (Scheme 4). When 2-(4-pyridylethynyl)-1,1′-biphenyl 3a was applied, higher temperature was required, generating desired product 4a in moderate yield. The reaction of 2-(3-thienylethynyl)-1, 1′-biphenyl 3b must be carried out at 0 °C, affording the corresponding cyclized product 4b in a low yield. Next, the reactivities of some arene-alkyne substrates that bear O, N, and simple methylene linkers were tested (Table 3). The reaction of phenyl 3-phenylpropiolate 5a gave the corresponding 3-nitro-4-phenyl-2H-chromen-2-one 6a in 34% isolated yield. However, the reaction temperature must be increased to 100 °C. The reaction of N,3-diphenylpropiolamide 5b under condition A did not proceed at all. Then, we attempted to run this reaction at 60 °C. Disappointingly, although 5b was totally consumed, no desired product was observed. For but-1-yne-1,4-diyldibenzene 5c, no desired product was formed either under condition A or at 0 °C. Furthermore, gram-scale application was successfully achieved. As shown in Scheme 5, 1000 mg of 1a could be efficiently transferred to 2a in 68% isolated yield. This example clearly demonstrated the operationally facileness of this method for organic synthesis. For further insight to be gained into the reaction mechanism, radical scavenger (TEMPO) was added to the reaction system. When 5 equiv of TEMPO was used, the reaction was suppressed, and only a trace amount of 2a was obtained (Scheme 6), suggesting that a radical intermediate might be involved in the key reaction step.16 On the basis of the results and literature precedents, a plausible mechanism was proposed as shown in Scheme 7. First, nitrogen dioxide was generated by thermal decomposition of Fe(NO3)3·9H2O.5c,17 Second, the in situ-generated nitrogen dioxide would give rise to two regiosiomeric alkenyl radicals 7 and 7′ by attack at either carbon of the alkyne moiety. Third, the favored six-membered ring radical intermediate 8 and the disfavored five-membered ring radical intermediate 8′ were formed from the corresponding intramolecular radical addition of 7 and 7′, respectively. Notably, the radical addition steps are generally reversible, which led to the result that favored intermediate 8 was afforded as the sole product. Subsequently, cyclohexadienyl radical 8 was oxidized by Fe3+ to form cyclohexadienyl cation 9.18 Notably, this single electron oxidation step would be the product-determining step. Finally, 9 would easily eliminate a proton to form final product 2.14a

reported. On the basis of our research interest in the construction of 9-functionalized phenanthrenes,15 we did research on Fe(NO3)3-participated nitration and cyclization of arenealkynes, which affords 9-nitrophenanthrenes efficiently. Herein, we wish to report our recent observation in this field. When optimizing the reaction conditions, 2-((4-methoxyphenyl)ethynyl)-1,1′-biphenyl 1a was chosen as the model substrate, and Fe(NO3)3·9H2O was applied as both nitro source and oxidant. We first examined the solvent effect carefully. As shown in Table 1, the desired reaction in Et3N, acetone, Table 1. Optimization of the Reaction Conditionsa

entry solvent 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17

Et3N acetone DCM toluene DCE MeOH THF MeCN MeNO2 MeNO2 MeNO2 MeNO2 MeNO2 MeNO2 MeNO2 MeNO2 MeNO2

Fe(NO3)3· temperature 9H2O (equiv) (°C) time (h) 3 3 3 3 3 3 3 3 3 4 5 2 1 0.5 2 2 2

30 30 30 30 30 30 30 30 30 30 30 30 30 30 0 60 100

24 24 24 24 24 24 24 10 3 3 3 3.5 5 48 7 1 0.5

NMR yield of 2a (%)b 0 (80)c 0 (63)c 0 (100)c 0 (99)c 0 (85)c 0 (96)c 15 (72)c 32 (0)c 61 (0)c 55 (0)c 37 (0)c 73 (0)c (71)d 52 (0)c 26 (32)c 0 (100)c 53 (0)c 10 (0)c

A solution of 1a (0.2 mmol) and Fe(NO3)3·9H2O in anhydrous solvent (3 mL) was stirred under an argon atmosphere. bThe yields were determined by 1H NMR (400 MHz) analysis of the crude reaction mixture with CH2Br2 (0.2 mmol) as internal standrad. cNMR recovery yield of 1a. dIsolated yield of 2a. a

DCM, toluene, DCE, or MeOH did not proceed at all (entries 1−6, Table 1). 10-(4-Methoxyphenyl)-9-nitrophenanthrene 2a could be observed in a low yield when THF or MeCN was used as the solvent (entries 7 and 8, Table 1). To our delight, 2a was obtained in a higher yield, when MeNO2 was used as the solvent (entry 9, Table 1). Thus, MeNO2 was chosen as the best solvent. Next, the amount of Fe(NO3)3·9H2O was optimized. An increased amount led to a decreased yield (entries 10 and 11, Table 1). When 2 equiv of Fe(NO3)3·9H2O was applied, 2a was formed in 71% isolated yield (entry 12, Table 1). Further reducing the amount of Fe(NO3)3·9H2O resulted in a much lower yield of 2a (entries 13 and 14, Table 1). Finally, the temperature effect was studied. No reaction occurred at lower temperature (entry 15, Table 1). When higher temperature was applied, the reaction speed was obviously accelerated; however, the corresponding yield was lower (entries 16 and 17, Table 1). Thus, condition A (Fe(NO3)3·9H2O (2 equiv), MeNO2, and 30 °C) was applied for the following studies. 10519

DOI: 10.1021/acs.joc.8b01201 J. Org. Chem. 2018, 83, 10518−10524

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The Journal of Organic Chemistry Table 2. Scope of This Reactiona

a A solution of 1a (0.2 mmol) and Fe(NO3)3·9H2O (2 equiv) in anhydrous MeNO2 (3 mL) was stirred under an argon atmosphere. Isolated yield was reported.

Scheme 4. Reaction with Heteroaromatic Substituents in the Alkyne Moiety

alkyne moiety. In this reaction, Fe(NO3)3·9H2O was used as both nitro source and oxidant.

In summary, we have developed a new strategy of nitration and cyclization of a series of arene-alkynes under mild conditions, which provides a novel and practical protocol for the synthesis of 9-nitrophenathrenes. The whole transformation was initiated by the radical addition of nitroxyl radical to the

General Methods. 1H (400 MHz) and 13C (100 MHz) NMR spectra of samples in CDCl3 were recorded on an AVANCE III 400 spectrometer. IR spectra were recorded on a Avatar 360 FT-IR spectro meter. HRMS (EI) determinations were carried out on a Waters GCT CA176 spectrometer. HRMS (ESI) determinations were carried out on a Bruker Daltonics APEXIII ESI-FTICRMS spectrometer. Melting points were determined on a WRS-2 apparatus. Anhydrous MeNO2 was distilled with CaSO4. Compounds 1a,15 1b,19 1d,15 1e,15 1f,15 1g,15 1h,15 1i,20 1j,15 1k,19 1l,19 5a,21 5b,21 and 5c22 were prepared according to literature procedures. General Procedure for the Synthesis of Arene-Alkynes. 2-Iodo-1,1′-biphenyl (1 equiv), aromatic alkyne (1 equiv), Pd(PPh3)4

■

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EXPERIMENTAL SECTION

DOI: 10.1021/acs.joc.8b01201 J. Org. Chem. 2018, 83, 10518−10524

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The Journal of Organic Chemistry Table 3. Reaction of Other Substratesa

(5 mol %), CuI (5 mol %), and Et3N (50 mL) were added subsequently to a 100 mL three-necked flask. The resulting mixture was refluxed and completed as monitored by TLC. Then, it was cooled to room temperature. The solvent was removed, and the residue was purified by flash chromatography on silica gel to afford 1c, 3a, or 3b. 2-((4-tert-Butylphenyl)ethynyl)-1,1′-biphenyl (1c). Liquid (827 mg, 62%); 1H NMR (400 MHz, CDCl3) δ 7.90−7.55 (m, 3 H), 7.52− 7.12 (m, 10 H), 1.29 (s, 9 H); 13C NMR (100 MHz, CDCl3) δ 151.3, 143.8, 140.6, 132.7, 131.1, 129.42, 129.39, 128.3, 127.8, 127.4, 127.0, 125.2, 121.8, 120.4, 92.4, 88.7, 34.7, 31.1; IR (neat) 2223, 2194, 1604, 1516, 1473, 1433 cm−1; HRMS (EI) calcd for C24H22 (M+) 310.1722, found 310.1724. 2-(4-Pyridylethynyl)-1,1′-biphenyl (3a).20 Solid (0.705 g, 28%); 1 H NMR (400 MHz, CDCl3) δ 8.52 (d, J = 4.8 Hz, 2 H), 7.72−7.53 (m, 3 H), 7.52−7.39 (m, 5 H), 7.37−7.29 (m, 1 H), 7.15 (d, J = 4.8 Hz, 2 H). 2-(3-Thienylethynyl)-1,1′-biphenyl (3b). Liquid (0.724 g, 28%); 1 H NMR (400 MHz, CDCl3) δ 7.69−7.54 (m, 3 H), 7.46−7.24 (m, 7 H), 7.20−7.11 (m, 1 H), 6.98 (dd, J = 5.0, 1.1 Hz, 1 H); 13 C NMR (100 MHz, CDCl3) δ 143.7, 140.5, 132.6, 129.5, 129.4, 129.3, 128.4, 128.2, 127.8, 127.4, 127.0, 125.2, 122.4, 121.5, 88.8, 87.5; IR (neat) 2209, 1598, 1575, 1527, 1476, 1433 cm−1; HRMS (EI) calcd for C18H13S (M + H+) 261.0732, found 261.0733. General Procedure for Reactions under Condition A. Substituted 2-phenylethynyl-1,1′-biphenyl 1a−l (0.20 mmol), Fe(NO3)3· 9H2O (0.40 mmol), and anhydrous nitromethane (3 mL) were added subsequently to 25 mL of the dry glass reaction tube, which was equipped with a magnetic stirrer. The mixture was stirred at 30 °C. The reaction was completed as monitored by TLC. The resulting reaction mixture was filtered. Then, the solvent was removed, and the residue was purified by flash column chromatography on silica gel (eluent: 100:1 petroleum ether/ethyl acetate) to afford 2a−2l, 4a, 4b, 6a, or 6c. Gram-Scale Synthesis. 2-((4-Methoxyphenyl)ethynyl)-1,1′-biphenyl 1a (1000 mg, 3.52 mmol), Fe(NO3)3·9H2O (2.841 g, 7.03 mmol), and anhydrous nitromethane (6 mL) were added subsequently to a 25 mL dry glass reaction tube equipped with a magnetic stirrer. The mixture was stirred at 30 °C. The reaction was completed after 4 h as monitored by TLC (eluent: 100:1 petroleum ether/ethyl acetate). The resulting reaction mixture was filtered. Then, the solvent was removed, and the residue was purified by flash column chromatography on silica gel (eluent: 100:1 petroleum ether/ethyl acetate) to afford 2a as a solid (788 mg, 68%). 10-(4-Methoxyphenyl)-9-nitrophenanthrene (2a). Solid (47 mg, 71%); mp 159.7−159.9 °C (ethyl acetate/petroleum ether); 1H NMR (400 MHz, CDCl3) δ 8.75 (t, J = 7.4 Hz, 2 H), 7.86−7.61 (m, 5 H), 7.59−7.48 (m, 1 H), 7.35 (d, J = 8.8 Hz, 2 H), 7.04 (d, J = 8.4 Hz, 2 H), 3.88 (s, 3 H); 13C NMR (100 MHz, CDCl3) δ 159.9, 131.1, 130.6, 130.38, 130.35, 129.8, 128.6, 128.4, 128.3, 128.1, 127.6, 125.6, 122.9, 122.81, 122.78, 122.5, 114.1, 55.3; IR (neat) 1607, 1558, 1537,

a A solution of 5 (0.2 mmol) and Fe(NO3)3·9H2O (2 equiv) in anhydrous MeNO2 (3 mL) was stirred under an argon atmosphere. Isolated yield was reported. bSome unidentified byproducts were formed.

Scheme 5. Gram Scale Reaction of 1a

Scheme 6. Control Reaction with 5 Equiv of TEMPO

Scheme 7. Proposed Mechanism

10521

DOI: 10.1021/acs.joc.8b01201 J. Org. Chem. 2018, 83, 10518−10524

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The Journal of Organic Chemistry 1433, 1388 cm−1; HRMS (ESI) calcd for C21H15NO3Na (M + Na+) 352.0944, found 352.0944. 10-(4-Acetylphenyl)-9-nitrophenanthrene (2b). Solid (50 mg, 70%); mp 193.5−193.6 °C (ethyl acetate/petroleum ether); 1H NMR (400 MHz, CDCl3) δ 8.78 (t, J = 7.6 Hz, 2 H), 7.90−7.67 (m, 4 H), 7.66−7.51 (m, 2 H), 7.45 (d, J = 8.4 Hz, 2 H), 7.27 (d, J = 8.4 Hz, 2 H), 2.37 (s, 3 H); 13C NMR (100 MHz, CDCl3) δ 169.2, 151.1, 131.1, 131.0, 130.5, 130.4, 130.2, 129.1, 128.62, 128.56, 128.4, 127.8, 123.0, 122.9, 122.7, 121.8, 21.2; IR (neat) 1766, 1592, 1528, 1503, 1488, 1452, 1430, 1406, 1378, 1366 cm−1; HRMS (EI) calcd for C22H15NO4 (M+) 357.1001, found 357.0995. 10-(4-tert-Butylphenyl)-9-nitrophenanthrene (2c). Solid (48 mg, 68%); mp 172.7−172.8 °C (ethyl acetate/petroleum ether); 1H NMR (400 MHz, CDCl3) δ 8.78 (t, J = 7.9 Hz, 2 H), 7.87−7.63 (m, 5 H), 7.62−7.47 (m, 3 H), 7.41−7.31 (m, 2 H), 1.40 (s, 9 H); 13C NMR (100 MHz, CDCl3) δ 151.7, 147.1, 130.5, 130.4, 130.1, 129.6, 129.0, 128.8, 128.4, 128.3, 128.1, 127.6, 125.5, 122.9, 122.8, 122.6, 34.8, 31.3; IR (neat) 1619, 1595, 1561, 1531, 1507, 1446, 1427, 1378 cm−1; HRMS (EI) calcd for C24H21NO2 (M+) 355.1572, found 355.1577. 9-Nitro-10-(4-phenylphenyl)phenanthrene (2d). Solid (49 mg, 65%); mp 195.6−195.8 °C (ethyl acetate/petroleum ether); 1H NMR (400 MHz, CDCl3) δ 8.80 (t, J = 7.2 Hz, 2 H), 7.86−7.65 (m, 9 H), 7.60 (t, J = 7.6 Hz, 1 H), 7.55−7.45 (m, 4 H), 7.40 (t, J = 7.4 Hz, 1 H); 13C NMR (100 MHz, CDCl3) δ147.2, 141.7, 140.4, 132.5, 130.5, 130.4, 130.3, 129.8, 128.9, 128.7, 128.5, 128.4, 128.3, 127.74, 127.67, 127.3, 127.2, 123.0, 122.9, 122.7, 122.6; IR (neat) 1601, 1564, 1531, 1461, 1446, 1382 cm−1; HRMS (EI) calcd for C26H17NO2 (M+) 375.1254, found 375.1250. 9-Nitro-10-phenylphenanthrene (2e). Solid (45 mg, 75%); mp 213.1−213.2 °C (ethyl acetate/petroleum ether); 1H NMR (400 MHz, CDCl3) δ 8.78 (t, J = 7.6 Hz, 2 H), 7.86−7.67 (m, 4 H), 7.66−7.48 (m, 5 H), 7.47−7.37 (m, 2 H); 13C NMR (100 MHz, CDCl3) δ 133.6, 130.5, 130.4, 130.3, 130.0, 129.9, 128.9, 128.64, 128.59, 128.5, 128.3, 128.2, 127.7, 122.9, 122.8, 122.7, 122.6; IR (neat) 1598, 1522, 1488, 1439, 1375 cm−1; HRMS (EI) calcd for C20H13NO2 (M+) 299.0946, found 299.0951. 10-(4-Chlorophenyl)-9-nitrophenanthrene (2f). Solid (33 mg, 50%); mp 196.4−196.9 °C (ethyl acetate/petroleum ether); 1H NMR (400 MHz, CDCl3) δ 8.78 (dd, J = 8.3, 5.1 Hz, 2 H), 7.87−7.66 (m, 4 H), 7.60−7.56 (m, 2 H), 7.52−7.48 (m, 2 H), 7.42−7.33 (m, 2 H); 13C NMR (100 MHz, CDCl3) δ 135.2, 132.1, 131.3, 130.6, 130.4, 129.9, 129.0, 128.8, 128.6, 128.48, 128.46, 128.3, 127.8, 123.0, 122.7, 122.6; IR (neat) 1531, 1488, 1446, 1375 cm−1; HRMS (EI) calcd for C20H12NO2Cl (M+) 333.0557, found 333.0561. 2-Chloro-10-nitro-9-phenylphenanthrene (2g). Solid (36 mg, 54%); mp 198.0−198.3 °C (ethyl acetate/petroleum ether); 1H NMR (400 MHz, CDCl3) δ 8.71 (d, J = 9.2 Hz, 2 H), 7.86−7.68 (m, 3 H), 7.66−7.47 (m, 5 H), 7.46−7.36 (m, 2 H); 13C NMR (100 MHz, CDCl3) δ 134.6, 133.3, 131.5, 130.2, 130.0, 129.8, 129.1, 128.91, 128.87, 128.8, 128.7, 128.0, 124.6, 123.8, 122.8, 122.0; IR (neat) 1598, 1531, 1482, 1443, 1378 cm−1; HRMS (EI) calcd for C20H12NO2Cl (M+) 333.0557, found 333.0550. 9-Nitro-10-(4-nitrophenyl)phenanthrene (2h). Solid (39 mg, 57%); mp 205.3−205.8 °C (ethyl acetate/petroleum ether); 1H NMR (400 MHz, CDCl3) δ 8.81 (d, J = 8.0 Hz, 2 H), 8.39 (d, J = 8.4 Hz, 2 H), 7.90−7.72 (m, 4 H), 7.70−7.55 (m, 3 H), 7.47 (d, J = 8.4 Hz, 1 H); 13C NMR (100 MHz, CDCl3) δ 148.3, 140.6, 131.2, 130.8, 130.5, 129.1, 128.96, 128.91, 128.7, 128.1, 127.9, 127.7, 123.8, 123.2, 123.1, 122.8, 122.3; IR (neat) 1671, 1592, 1522, 1446, 1430 cm−1; HRMS (EI) calcd for C20H12N2O4 (M+) 344.0792, found 344.0789. 10-(4-Cyanophenyl)-9-nitrophenanthrene (2i). Solid (36 mg, 55%); mp 202.2−202.4 °C (ethyl acetate/petroleum ether); 1H NMR (400 MHz, CDCl3) δ 8.81 (dd, J = 8.4, 1.2 Hz, 2 H), 7.89−7.70 (m, 6 H), 7.69−7.52 (m, 3 H), 7.46 (dd, J = 8.4, 0.8 Hz, 1 H); 13 C NMR (100 MHz, CDCl3) δ 138.7, 132.4, 130.9, 130.8, 130.5, 129.2, 128.90, 128.85, 128.7, 128.1, 128.03, 127.98, 123.2, 123.0, 122.8, 122.4, 118.3, 113.1; IR (neat) 2226, 1604, 1528, 1503, 1446, 1427 cm−1; HRMS (EI) calcd for C21H13N2O2 (M + H+) 325.0972, found 325.0971.

3-Methyl-9-(4-methoxyphenyl)-10-nitrophenanthrene (2j). Solid (52 mg, 75%); mp 173.1−173.5 °C (ethyl acetate/petroleum ether); 1H NMR (400 MHz, CDCl3) δ 8.75 (d, J = 8.0 Hz, 1 H), 8.56 (s, 1 H), 7.78−7.70 (m, 1 H), 7.68−7.60 (m, 2 H), 7.59−7.51 (m, 2 H), 7.35 (d, J = 8.8 Hz, 2 H), 7.04 (d, J = 8.8 Hz, 2 H), 3.89 (s, 3 H), 2.66 (s, 3 H); 13C NMR (100 MHz, CDCl3) δ 159.9, 138.3, 131.2, 130.8, 130.5, 130.1, 130.0, 128.7, 128.6, 128.1, 127.5, 125.7, 122.8, 122.7, 122.4, 120.8, 114.1, 55.3, 22.1; IR (neat) 1610, 1592, 1525, 1500, 1430 cm−1; HRMS (EI) calcd for C22H17NO3 (M+) 343.1208, found 343.1204. 6-Methyl-10-(4-methoxyphenyl)-2,9-dinitrophenanthrene (2k). Solid (48 mg, 62%); mp 254.2−254.5 °C (ethyl acetate/petroleum ether); 1 H NMR (400 MHz, CDCl3) δ 8.86 (d, J = 9.2 Hz, 1 H), 8.68−8.51 (m, 2 H), 8.47 (dd, J = 9.2, 2.0 Hz, 1 H), 7.66 (s, 2 H), 7.34 (d, J = 8.4 Hz, 2 H), 7.07 (d, J = 8.8 Hz, 2 H), 3.92 (s, 3 H), 2.69 (s, 3 H); 13 C NMR (100 MHz, CDCl3) δ 160.4, 146.6, 139.5, 133.9, 132.0, 131.2, 130.9, 129.5, 128.9, 124.5, 124.3, 124.0, 123.6, 122.9, 122.0, 121.7, 114.6, 55.3, 22.1; IR (neat) 1610, 1534, 1507, 1494, 1467, 1439 cm−1; HRMS (EI) calcd for C22H16N2O5 (M+) 388.1059, found 388.1062. 2-Cyano-6-methyl-10-(4-methoxyphenyl)-9-nitrophenanthrene (2l). Solid (50 mg, 68%); mp 254.9−255.0 °C (ethyl acetate/petroleum ether); 1H NMR (400 MHz, CDCl3) δ 8.81 (d, J = 8.8 Hz, 1 H), 8.54 (s, 1 H), 7.99 (s, 1 H), 7.89 (d, J = 8.8 Hz, 1 H), 7.64 (s, 2 H), 7.31 (d, J = 8.8 Hz, 2 H), 7.06 (d, J = 8.8 Hz, 2 H), 3.91 (s, 3 H), 2.68 (s, 3 H); 13C NMR (100 MHz, CDCl3) δ 160.3, 148.3, 139.3, 133.6, 132.5, 131.7, 131.1, 130.8, 129.6, 129.4, 128.0, 124.0, 123.2, 122.8, 121.7, 118.6, 114.5, 111.0, 55.4, 22.1; IR (neat) 2226, 1610, 1528, 1510, 1455, 1439 cm−1; HRMS (EI) calcd for C23H16N2O3 (M+) 368.1161, found 368.1164. 10-(4-Pyridyl)-9-nitrophenanthrene (4a). Solid (39 mg, 65%); mp 147.7−147.9 °C (ethyl acetate/petroleum ether); 1H NMR (400 MHz, CDCl3) δ 8.83 (s, 4 H), 7.95−7.74 (m, 4 H), 7.62 (t, J = 7.6 Hz, 1 H), 7.52 (d, J = 8.2 Hz, 1 H), 7.42 (s, 2 H); 13C NMR (100 MHz, CDCl3) δ 150.1, 130.5, 129.0, 128.9, 128.8, 128.7, 128.1, 128.0, 125.0, 123.2, 123.1, 122.9, 122.4; IR (neat) 1592, 1529, 1496, 1450 cm−1; HRMS (ESI) calcd for C19H13N2O2 (M + H+) 301.0978, found 301.0972. 10-(3-Thienylethynyl)-9-nitrophenanthrene (4b). Oil (19 mg, 31%); 1 H NMR (400 MHz, CDCl3) δ 8.86−8.72 (m, 2 H), 7.86−7.67 (m, 5 H), 7.65−7.57 (m, 1 H), 7.55−7.43 (m, 2 H), 7.27−7.21 (m, 1 H); 13C NMR (100 MHz, CDCl3) δ 132.9, 130.5, 130.33, 130.31, 129.9, 129.4, 128.9, 128.5, 128.3, 127.8, 126.15, 126.08, 125.5, 123.0, 122.9, 122.8, 122.6; IR (neat) 1601, 1529, 1496, 1450 cm−1; HRMS (EI) calcd for C18H12NO2S (M + H+) 306.0583, found 306.0582. 3-Nitro-4-phenyl-2H-chromen-2-one (6a). Solid (18 mg, 34%); mp 116.1−116.2 °C (ethyl acetate/petroleum ether); 1H NMR (400 MHz, CDCl3) δ 7.74−7.65 (m, 1 H), 7.60−7.52 (m, 3 H), 7.49 (d, J = 8.4 Hz, 1 H), 7.41−7.37 (m, 2 H), 7.34−7.29 (m, 2 H); 13 C NMR (100 MHz, CDCl3) δ 153.4, 152.9, 147.0, 134.1, 130.8, 129.2, 128.8, 127.9, 125.5, 117.9, 117.5; IR (neat) 1736, 1604, 1567, 1532, 1448 cm−1; HRMS (EI) calcd for C15H10NO4 (M + H+) 268.0604, found 268.0604.

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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.8b01201. 1

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H and 13C NMR spectra of all the products (PDF)

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Yanbin Zhang: 0000-0002-4087-420X Hao Guo: 0000-0003-3314-4564 Notes

The authors declare no competing financial interest. 10522

DOI: 10.1021/acs.joc.8b01201 J. Org. Chem. 2018, 83, 10518−10524

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The Journal of Organic Chemistry

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ACKNOWLEDGMENTS We greatly acknowledge the financial support from Fundamental Research Funds for the Central Universities, Pioneering Project of Academy for Engineering and Technology, Fudan University (gyy2017-002).

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DOI: 10.1021/acs.joc.8b01201 J. Org. Chem. 2018, 83, 10518−10524

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DOI: 10.1021/acs.joc.8b01201 J. Org. Chem. 2018, 83, 10518−10524