Construction of Polysubstituted 1,2-Dihydrocyclobuta[b]naphthalenes

May 16, 2017 - A facile protocol for the synthesis of polysubstituted 1,2-dihydrocyclobuta[b]naphthalenes and 1,2-dihydrocyclobuta[b]anthracenes was ...
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Construction of Polysubstituted 1,2-Dihydrocyclobuta[b]naphthalenes and 1,2-Dihydrocyclobuta[b]anthracenes with Photoluminescence Dianpeng Chen,†,‡ Lianpeng Zhang,*,‡ Jinzhong Yao,‡ and Hongwei Zhou*,†,‡ †

Department of Chemistry, Zhejiang University (Campus Xixi), Hangzhou 310028, People’s Republic of China College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing 314001, People’s Rupublic of China

‡

S Supporting Information *

ABSTRACT: A facile protocol for the synthesis of polysubstituted 1,2-dihydrocyclobuta[b]naphthalenes and 1,2dihydrocyclobuta[b]anthracenes was developed via a sequence of base-promoted 1,5-H shift, intramolecular [2 + 2] cycloaddition, and aromatization. The synthesized 1,2-dihydrocyclobuta[b]anthracenes exhibited bright blue emissions in solution and strong yellow emissions in solid, which made them possible candidates for optoelectronic conjugated materials.

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INTRODUCTION The four-membered ring frameworks are present in numerous important compounds, and polysubstituted cyclobutanes, as a vital class of four-membered rings, have attracted considerable interest for their unique physiological activities1 and applications in organic synthesis.2 Certain famous molecules in the cyclobutane family, for example, iannotinidine F,3 pestalotiopsin,4 cyclobut-G,5 and sceptrin,6 occupy a prominent place in biological and medicinal chemistry. Generally, there are only two ways to construct cyclobutane rings: ring-closure strategy or [2 + 2] cycloaddition strategy (Scheme 1a).7 However, ring-closure strategy might encounter difficulty in some cases because of its inherent ring strain. Accordingly, developing new and effective [2 + 2] cycloaddition methods for the construction of newly formed cyclobutanes remains a formidable challenge. Propargyl allenyl isomerizations have attracted much attention for the organic community, in which the allene moiety could be thought as an “activated olefin”, generally enhancing the possibility of reaction compared with a normal olefin.8 During our research on organosulfur chemistry,9 we found that alkynyl allyl sulfones could offer corresponding allenes via basepromoted 1,5-H shift (Scheme 1b),9a which might provide an efficient way to construct a highly substituted cyclobutane by a cycloaddition using the allene moiety. Herein, we report a sequence of propargyl allenyl isomerization, intramolecular [2 + 2] cycloaddition, and aromatization, yielding highly functionalized 1,2-dihydrocyclobuta[b]naphthalenes and 1,2-dihydrocyclobuta[b]anthracenes, which are difficult to prepare by other methods (Scheme 1c).

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3-(4-chlorophenyl)-1-(2-iodophenyl)prop-2-ynyl acetate with (E)-1-chloro-4-(2-methylpent-2-en-4-ynylsulfonyl)benzene under Sonogashira conditions. Our study was initiated by testing the reaction of 1a in the presence of triethylamine (TEA) in acetonitrile at room temperature. To our delight, this set of conditions afforded the expected four-membered product 2a in 35% yield (Table 1, entry 1), and the structure was revealed by X-ray diffraction.10 Then we began to optimize the reaction with respect to different bases, solvents, and temperatures. Replacing TEA by DIPEA (N,N-diisopropylethylamine) gave similar yields (Table 1, entries 2), and the stronger organic base DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) afforded an unidentified mixture (Table 1, entries 3). Inorganic bases, such as K2CO3 and Na2CO3, showed poor reactivity and gave 2a in 13−16% yields (Table 1, entries 4 and 5). Whereas subsequent screening of other common solvents, such as THF, 1,4-dioxane, toluene, and DMF, did not improve the yield obviously, DCE was found to be an appropriate solvent for this reaction that afforded the product in 57% yield (Table 1, entries 6−10). In addition, increasing the reaction temperature to 80 °C offered a more satisfactory yield of 82% (Table 1, entry 12). Thus, the optimized reaction conditions were chosen as follows: 0.5 mmol of 1a and 1.5 mmol of TEA in 2 mL of DCE were stirred at 80 °C. With the optimized conditions in hand, the scope of this reaction was investigated further (Table 2). The R1 could be an acetoxyl group (Table 2, 2a−2j), benzoyloxy group (Table 2, 2k), or methoxy group (Table 2, 2l,m), and the yields were satisfactory. The R2 could be phenyl groups optionally substituted with an electron-withdrawing (Table 2, 2a,b, 2g, 2j,k) or an electron-donating group (Table 2, 2c,d, 2i). Unfortunately, we failed to obtain target products when R2 was an alkyl group,

RESULTS AND DISCUSSION

As a first attempt, we chose 1a as the starting material, which could be readily prepared via the treatment of © 2017 American Chemical Society

Received: March 31, 2017 Published: May 16, 2017 6202

DOI: 10.1021/acs.joc.7b00762 J. Org. Chem. 2017, 82, 6202−6209

Article

The Journal of Organic Chemistry Scheme 1. Proposal for the Construction of Cyclobutanes

Table 1. Optimization of the Reaction Conditionsa

entry

base (equiv)

solvent

T (°C)

yield (%)

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

TEA (3.0) DIPEA (3.0) DBU (3.0) K2CO3 (3.0) Na2CO3 (3.0) TEA (3.0) TEA (3.0) TEA (3.0) TEA (3.0) TEA (3.0) TEA (3.0) TEA (3.0) TEA (3.0)

MeCN MeCN MeCN MeCN MeCN THF dioxane PhMe DMF DCE DCE DCE DCE

rt rt rt rt rt rt rt rt rt rt 60 80 100

35 31 0 13 16 48 33 29 34 57 65 82 53

[Scheme 2, (1)]. Then, we prepared 1a-d2 as the substrate for the isotopic labeling experiment and found that one of the deuterium atoms on the methylene group moved to the naphthalene ring of 2a, also implying the occurrence of 1,5-H shift [Scheme 2, (2)]. Based on these results, we proposed a plausible pathway, as shown in Scheme 3. The electron-deficient allene intermediate A, in situ generated from 1,5-H shift, undergoes intramolecular [2 + 2] cycloaddition in a [2a + 2s] mode offering intermediate B. Then intermediate C is formed via aromatization, which experiences the rearrangement of double bond to furnish product (Scheme 3). During the preparation of 2 and 4, we anticipated that these compounds might exhibit emission under UV light (365 nm), due to the fact that the alkylidene-1,2-dihydrocyclobuta[b]naphthalenes/anthracenes were new fluorophores, which might have the potential in optoelectronic devices, luminescent sensors, and biomedical imaging.12 Therefore, we investigated the photophysical properties of these compounds (Figure 1). Absorption of the selected compounds 2g, 2k, 4b, and 4e were measured in dilute solution of THF in a concentration scale of 10−5 M. The excitation spectra of 2g, 2k, 4b, and 4e was done (see Supporting Information). Compounds 2g and 2k absorbed light at about 320 nm, and the substituent effect was not apparent. The excitation wavelengths of 2g and 2k were 320 and 323 nm. When 4b and 4e were measured, we found that the maximum absorption wavelength (λmax = 380 nm) had an 80 nm red shift, probably due to the extending of the conjugated unsaturated system. However, the substituent effect was not apparent yet. The excitation wavelengths of 4b and 4e were 379 and 380 nm. 2g and 2k emitted bright blue light at about 366 nm with a Stokes shift at about 46 nm, compared to 4b and 4e which emitted bright light at about 400 nm with a large Stokes shift about 60 nm. Quantum yield of 2g was 11.66%, referring to the standard of 2-aminopyridine (Φ = 0.60 in 0.1 M H2SO4). With the increase of the conjugated system, the quantum yields of 4b and 4e were found to be 43.27 and 40.71%, respectively, referring to the standard of quinine sulfate (Φ = 0.54 in 0.1 M H2SO4). The emission lifetimes of 4b and 4e were 6.97 and 7.04 ns, which were measured using time-correlated singlephoton counting (see Supporting Information). When we measured the absorption and emission of 4b and 4e, we observed that the emission of dilute solutions changed by just adding water. The maximum emission wavelength was gradually red-shifted as the water fraction gradually changed from

a Conditions: 0.5 mmol of 1a and 1.5 mmol of TEA in 2 mL of DCE were stirred at 80 °C.

indicating that the cyclic intermediates might be stabilized by aryl groups. Then our attention was diverted to the synthesis of polysubstituted 1,2-dihydrocyclobuta[b]anthracene derivatives, which might have a value of application in materials science because of its novel conjugated system.11 We prepared 3a and treated it with TEA in DCE at 80 °C. Gratifyingly, the expected 4a was obtained in 77% yield (Table 3, 4a). Correspondingly, a series of 1,2-dihydrocyclobuta[b]anthracenes were synthesized in good yields (Table 3, 4a−4e). Although we did not observe the allene intermediate shown in Scheme 1c, we conducted the control experiment by treating 1a with 20 equiv of CD3OD under similar conditions. The protons of the naphthalene ring and the α-carbon of the sulfonyl group were deuterated, showing that the process of base-promoted 1,5-H shift experiences proton exchange with the reaction system 6203

DOI: 10.1021/acs.joc.7b00762 J. Org. Chem. 2017, 82, 6202−6209

Article

The Journal of Organic Chemistry Table 2. Synthesis of 1,2-Dihydrocyclobuta[b]naphthalene Derivativesa

a

Conditions: substrate 1 (0.5 mmol) and TEA (1.5 mmol) in 2 mL of DCE were stirred at 80 °C for 8 h.

and 1,2-dihydrocyclobuta[b]anthracenes via a sequence of basepromoted 1,5-H shift, intramolecular [2 + 2] cycloaddition, and aromatization. Moreover, the new fluorophore of 2-(propan-2ylidene)-1,2-dihydrocyclobuta[b]anthracene and its photophysical properties were investigated. Further studies on the synthetic application are currently ongoing.

0 to 70%, which was consistent with a gradually increased fluorescent intensity (Figure 2a). When the ratio of water in THF increased to 80%, bright green emission of 4b was seen under UV light (Figure 2b). As water fraction increased to 90%, the emission wavelength of 4b was about 500 nm, and the color variation under UV light (365 nm) was significant. We supposed that adding water to the solution of 4b in THF resulted in the aggregation of solutes and the formation of nanoparticles. The size distribution of nanoparticles was determined by DLS. As the water fraction was 90%, the average diameter of nanoparticles was 144 nm (see Supporting Information). Compounds 4b and 4e had strong emission not only in nanosuspensions but also in solids. Then we measured the solid emission of 4b and 4e, and the emission wavelength of these two compounds was about 500 nm (Figure 3a). Compound 4b was shining in solid. Before and after UV irradiation on 4b is shown in Figure 3b.

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EXPERIMENTAL SECTION

General Information. All reactions were carried out in oven-dried glassware sealed with rubber septa under nitrogen condition. All solvents were distilled under nitrogen atmosphere prior to use. THF was dried over sodium, and toluene was dried over sodium. Purification of products was conducted by flash chromatography on silica gel (200−300 mesh). Chemical shifts are reported in parts per million (s = singlet, d = doublet, t = triplet, q = quartet, dd = doublet of doublets, m = multiplet). Absorption and emission spectra of these compounds in solutions were measured in THF with a concentration scale of 10−5 M. Typical Procedure for the Synthesis of 2a. Substrate 1a (0.5 mmol, 1.0eq) was successively added to a 25 mL vial equipped with a stir bar. Et3N (150 mg, 1.5 mmol, 3.0 equiv) in DCE (2.0 mL) was added to the system using a syringe. The reaction was stirred at 80 °C for 8 h.

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CONCLUSIONS In conclusion, we have developed a facile protocol for the synthesis of polysubstituted 1,2-dihydrocyclobuta[b]naphthalenes 6204

DOI: 10.1021/acs.joc.7b00762 J. Org. Chem. 2017, 82, 6202−6209

Article

The Journal of Organic Chemistry Table 3. Synthesis of 1,2-Dihydrocyclobuta[b]anthracene Derivativesa

a

Conditions: substrate 1 (0.5 mmol) and TEA (1.5 mmol) in 2 mL of DCE were stirred at 80 °C for 8 h.

Scheme 2. Deuterium Labeling Studies

(E)-2-(4-Chlorophenyl)-1-(1-tosylpropan-2-ylidene)-1,2-dihydrocyclobuta[b]naphthalen-3-yl Acetate (2b): Light yellow powder, 196 mg, 76% yield, mp 127−128 °C; 1H NMR (400 MHz, CDCl3) δ 7.88 (dd, J = 5.0, 3.0 Hz, 2H), 7.70 (d, J = 8.0 Hz, 2H), 7.62 (s, 1H), 7.48 (dd, J = 5.0, 3.0 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.24−7.15 (m, 2H), 6.94 (d, J = 8.0 Hz, 2H), 4.07 (s, 1H), 3.61 (d, J = 14.0 Hz, 1H), 3.53 (d, J = 14.0 Hz, 1H), 2.46 (s, 3H), 2.26 (s, 3H), 2.13 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 167.2, 145.5, 143.6, 141.7, 138.1, 137.3, 135.6, 135.4, 133.8, 133.0, 129.9, 129.1, 128.9, 128.8, 128.4, 127.5, 126.2, 126.2, 121.3, 119.2, 116.8, 60.9, 53.9, 21.7, 20.5, 20.1; IR (neat) 3497, 1716, 768 cm−1; HRMS (EI-TOF) calcd for C30H25ClO4S 516.1162, found 516.1165. (E)-2-p-Tolyl-1-(1-tosylpropan-2-ylidene)-1,2-dihydrocyclobuta[b]naphthalen-3-yl Acetate (2c): Light yellow powder, 210 mg, 85% yield, mp 125−126 °C; 1H NMR (400 MHz, CDCl3) δ 7.87 (m, 2H), 7.72 (d, J = 9.0 Hz, 2H), 7.61 (s, 1H), 7.49−7.43 (m, 2H), 7.35

Upon completion, the reaction was quenched with water, and the mixture was extracted with DCM and dried over anhydrous Na2SO4. After evaporation, chromatography on silica gel (5:1 petroleum ether/ ethyl acetate) of the reaction mixture afforded 2a as a light yellow powder (220 mg, 82%). (E)-2-(4-Chlorophenyl)-1-(1-(4-chlorophenylsulfonyl)propan-2ylidene)-1,2-dihydrocyclobuta[b]naphthalen-3-yl Acetate (2a): Light yellow powder, 220 mg, 82% yield, mp 132−133 °C; 1H NMR (400 MHz, CDCl3) δ 7.93−7.85 (m, 2H), 7.74−7.68 (m, 2H), 7.63 (s, 1H), 7.54−7.46 (m, 4H), 7.24−7.17 (m, 2H), 6.98 (d, J = 8.0 Hz, 2H), 4.47 (s, 1H), 3.67 (d, J = 14.0 Hz, 1H), 3.57 (d, J = 14.0 Hz, 1H), 2.23 (s, 3H), 2.15 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 167.3, 144.0, 141.6, 140.9, 138.3, 137.3, 137.2, 135.6, 133.6, 133.1, 129.7, 129.6, 129.1, 129.0, 128.8, 127.6, 126.3, 126.2, 121.4, 118.4, 116.9, 60.8, 54.3, 20.5, 20.0; IR (neat) 3497, 1718, 772 cm−1; HRMS (EI-TOF) calcd for C29H22Cl2O4S 536.0616, found 536.0615. 6205

DOI: 10.1021/acs.joc.7b00762 J. Org. Chem. 2017, 82, 6202−6209

Article

The Journal of Organic Chemistry Scheme 3. Plausibe Mechanism

Figure 1. Absorption and emission spectra of 2g, 2k, 4b, and 4e.

Figure 2. (a) Emission spectra of 4b in THF/water mixtures. (b) Solution color of 4b under UV light (365 nm). Excited width = 2.5 nm, emission width = 2.5 nm. 116.6, 60.9, 54.1, 21.7, 21.2, 20.5, 20.0; IR (neat) 3493, 1728, 768 cm−1; HRMS (EI-TOF) calcd for C31H28O4S 496.1708, found 496.1710. (E)-1-(1-(4-Chlorophenylsulfonyl)propan-2-ylidene)-2-p-tolyl-1,2dihydrocyclobuta[b]naphthalen-3-yl Acetate (2d): Light yellow powder, 209 mg, 81% yield, mp 127−128 °C; 1H NMR (400 MHz,

(d, J = 8.0 Hz, 2H), 7.02 (d, J = 8.0 Hz, 2H), 6.85 (d, J = 8.0 Hz, 2H), 3.89 (s, 1H), 3.69 (d, J = 14.0 Hz, 1H), 3.52 (d, J = 14.0 Hz, 1H), 2.47 (s, 3H), 2.30 (s, 3H), 2.27 (s, 3H), 2.11 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 167.3, 145.4, 144.1, 141.9, 138.1, 136.9, 135.5, 135.4, 135.3, 134.7, 129.9, 129.4, 128.8, 128.5, 127.6, 127.5, 126.0, 125.9, 121.2, 118.8, 6206

DOI: 10.1021/acs.joc.7b00762 J. Org. Chem. 2017, 82, 6202−6209

Article

The Journal of Organic Chemistry

Figure 3. (a) Solid emission spectra of 4b and 4e. (b) Images of compound 4b under white light (left) and under UV light (365 nm) (right). CDCl3) δ 7.90−7.85 (m, 2H), 7.76−7.70 (m, 2H), 7.62 (s, 1H), 7.53− 7.49 (m, 2H), 7.49−7.43 (m, 2H), 7.04 (d, J = 8.0 Hz, 2H), 6.89 (d, J = 8.0 Hz, 2H), 4.29 (s, 1H), 3.74 (d, J = 14.0 Hz, 1H), 3.56 (d, J = 14.0 Hz, 1H), 2.31 (s, 3H), 2.25 (s, 3H), 2.13 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 167.4, 144.5, 141.8, 140.9, 138.2, 137.2, 137.0, 135.6, 135.4, 134.4, 129.9, 129.5, 129.4, 128.8, 127.6, 127.5, 126.2, 126.1, 121.3, 118.1, 116.8, 60.8, 54.5, 21.2, 20.5, 20.0; IR (neat) 3496, 1726, 765 cm−1; HRMS (EI-TOF) calcd for C30H25ClO4S 516.1162, found 516.1165. (E)-2-Phenyl-1-(1-tosylpropan-2-ylidene)-1,2-dihydrocyclobuta[b]naphthalen-3-yl Acetate (2e): Light yellow powder, 169 mg, 70% yield, mp 120−121 °C; 1H NMR (400 MHz, CDCl3) δ 7.90−7.83 (m, 2H), 7.72 (d, J = 8.0 Hz, 2H), 7.62 (s, 1H), 7.50−7.42 (m, 2H), 7.36 (d, J = 8.0 Hz, 2H), 7.22 (dd, J = 7.0, 3.0 Hz, 3H), 6.98 (dd, J = 8.0, 2.0 Hz, 2H), 3.96 (s, 1H), 3.68 (d, J = 14 Hz, 1H), 3.53 (d, J = 14 Hz, 1H), 2.47 (s, 3H), 2.28 (s, 3H), 2.10 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 167.2, 145.5, 143.9, 141.9, 138.6, 138.1, 135.6, 135.3, 134.4, 129.9, 128.8, 128.7, 128.5, 127.6, 127.5, 127.3, 126.1, 126.0, 121.2, 118.9, 116.7, 60.9, 54.4, 21.7, 20.5, 20.0; IR (neat) 3495, 1718, 761 cm−1; HRMS (EI-TOF) calcd for C30H26O4S 482.1552, found 482.1555. (E)-1-(1-(4-Chlorophenylsulfonyl)propan-2-ylidene)-2-phenyl1,2-dihydrocyclobuta[b]naphthalen-3-yl Acetate (2f): Light yellow powder, 196 mg, 78% yield, mp 123−124 °C; 1H NMR (400 MHz, CDCl3) δ 7.91−7.85 (m, 2H), 7.77−7.70 (m, 2H), 7.63 (s, 1H), 7.55− 7.50 (m, 2H), 7.49−7.41 (m, 2H), 7.26−7.22 (m, 3H), 7.03 (dd, J = 8.0, 2.0 Hz, 2H), 4.36 (s, 1H), 3.72 (d, J = 14 Hz, 1H), 3.57 (d, J = 14 Hz, 1H), 2.25 (s, 3H), 2.11 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 167.3, 144.3, 141.7, 140.9, 138.5, 138.3, 137.2, 135.6, 134.2, 129.8, 129.6, 128.8, 127.7, 127.6, 127.4, 126.2, 126.1, 121.3, 118.2, 116.8, 60.8, 54.8, 20.5, 20.0; IR (neat) 3496, 1726, 775 cm−1; HRMS (EI-TOF) calcd for C29H23ClO4S 502.1006, found 502.1004. (E)-1-(1-(4-Chlorophenylsulfonyl)propan-2-ylidene)-2-(4-fluorophenyl)-1,2-dihydrocyclobuta[b]naphthalen-3-yl Acetate (2g): Light yellow powder, 190 mg, 73% yield, mp 137−138 °C; 1H NMR (400 MHz, CDCl3) δ 7.88 (dd, J = 5.0, 3.0 Hz, 2H), 7.74 (dd, J = 9.0, 3.0 Hz, 2H), 7.63 (s, 1H), 7.54−7.46 (m, 4H), 7.06−6.98 (m, 2H), 6.94 (m, 2H), 4.45 (s, 1H), 3.68 (d, J = 14.0 Hz, 1H), 3.56 (d, J = 14.0 Hz, 1H), 2.23 (s, 3H), 2.14 (d, J = 2.6 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 167.3, 162.0 (J = 245 Hz), 144.3, 141.6, 140.9, 138.3, 137.3, 135.6, 134.4 (J = 30 Hz), 133.9, 129.8, 129.6, 129.3, 129.2, 128.8, 127.6, 126.3 (J = 8 Hz), 121.3, 118.3, 116.9, 115.7 (J = 21 Hz), 60.8, 54.1, 20.5, 20.0; IR (neat) 3485, 1716, 778 cm−1; HRMS (EI-TOF) calcd for C29H22ClFO4S 520.0911, found 520.0913. (E)-2-Phenyl-1-(1-tosylbutan-2-ylidene)-1,2-dihydrocyclobuta[b]naphthalen-3-yl Acetate (2h): Light yellow powder, 193 mg, 78% yield, mp 115−116 °C; 1H NMR (400 MHz, CDCl3) δ 7.87 (m, 2H), 7.72 (d, J = 8.0 Hz, 2H), 7.61 (s, 1H), 7.46 (dd, J = 7.0, 3.0 Hz, 2H), 7.36 (d, J = 8.0 Hz, 2H), 7.22 (m, 3H), 6.99 (d, J = 7.0 Hz, 2H), 3.99 (s, 1H), 3.66 (d, J = 14.0 Hz, 1H), 3.57 (d, J = 14.0 Hz, 1H), 2.81 (dd, J = 14.0, 7.0 Hz, 1H), 2.63 (dd, J = 14.0, 7.0 Hz, 1H), 2.47 (s, 3H), 2.10 (s, 3H), 1.21 (t, J = 8.0 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 167.2, 145.4, 143.7, 141.6, 138.6, 138.1, 135.6, 135.4, 134.6, 129.9, 128.8, 128.6, 127.5, 127.3, 126.1, 126.0, 125.1, 121.2, 116.8, 57.9, 54.3, 26.2, 21.7, 20.5, 12.2; IR (neat) 3484, 1718, 785 cm−1; HRMS (EI-TOF) calcd for C31H28O4S 496.1708, found 496.1706.

(E)-2-p-Tolyl-1-(1-tosylbutan-2-ylidene)-1,2-dihydrocyclobuta[b]naphthalen-3-yl Acetate (2i): Light yellow powder, 204 mg, 80% yield, mp 118−119 °C; 1H NMR (400 MHz, CDCl3) δ 7.90−7.84 (m, 2H), 7.73 (d, J = 8.0 Hz, 2H), 7.61 (s, 1H), 7.48−7.43 (m, 2H), 7.36 (d, J = 8.0 Hz, 2H), 7.04 (d, J = 8.0 Hz, 2H), 6.88 (d, J = 8.0 Hz, 2H), 3.93 (s, 1H), 3.67 (d, J = 14.0 Hz, 1H), 3.60 (d, J = 14.0 Hz, 1H), 2.81 (dd, J = 14.0, 7.0 Hz, 1H), 2.64 (dd, J = 14.0, 7.0 Hz, 1H), 2.47 (s, 3H), 2.31 (s, 3H), 2.12 (s, 3H), 1.22 (t, J = 8.0 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 167.3, 145.4, 143.9, 141.6, 138.0, 136.9, 135.6, 135.5, 135.4, 134.9, 129.9, 129.5, 128.8, 128.6, 127.5, 127.4, 126.1, 125.9, 124.9, 121.2, 116.7, 57.9, 53.9, 26.2, 21.7, 21.2, 20.5, 12.2; IR (neat) 3488, 1719, 781 cm−1; HRMS (EI-TOF) calcd for C32H30O4S 510.1865, found 510.1863. (E)-2-(4-Chlorophenyl)-1-(1-tosylbutan-2-ylidene)-1,2-dihydrocyclobuta[b]naphthalen-3-yl Acetate (2j): Light yellow powder, 201 mg, 76% yield, mp 122−123 °C; 1H NMR (400 MHz, CDCl3) δ 7.88 (m, 2H), 7.70 (d, J = 8.0 Hz, 2H), 7.61 (s, 1H), 7.50−7.44 (m, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H), 6.95 (d, J = 8.0 Hz, 2H), 4.11 (s, 1H), 3.66 (d, J = 14.0 Hz, 1H), 3.52 (d, J = 14.0 Hz, 1H), 2.80 (dd, J = 14.0, 8.0 Hz, 1H), 2.65−2.54 (dd, J = 14.0, 8.0 Hz, 1H), 2.46 (s, 3H), 2.14 (s, 3H), 1.20 (t, J = 8.0 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 167.2, 145.5, 143.4, 141.5, 138.1, 137.4, 135.6, 135.5, 134.0, 133.0, 129.9, 129.0, 128.9, 128.8, 128.5, 127.5, 126.2, 126.2, 125.3, 121.3, 116.9, 57.9, 53.7, 26.3, 21.7, 20.5, 12.2; IR (neat) 3489, 1716, 773 cm−1; HRMS (EI-TOF) calcd for C31H27ClO4S 530.1319, found 530.1316. (E)-2-(4-Chlorophenyl)-1-(1-tosylpropan-2-ylidene)-1,2-dihydrocyclobuta[b]naphthalen-3-yl 4-Methylbenzoate (2k): Light yellow powder, 198 mg, 67% yield, mp 131−132 °C; 1H NMR (400 MHz, CDCl3) δ 7.96 (m, 3H), 7.92−7.88 (m, 1H), 7.71 (d, J = 8.0 Hz, 2H), 7.66 (s, 1H), 7.50−7.43 (m, 2H), 7.37 (d, J = 8.0 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 7.07 (d, J = 8.0 Hz, 2H), 6.88 (d, J = 8.0 Hz, 2H), 4.07 (s, 1H), 3.63 (d, J = 14.0 Hz, 1H), 3.56 (d, J = 14.0 Hz, 1H), 2.51 (s, 3H), 2.45 (s, 3H), 2.30 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 163.3, 145.6, 144.6, 143.5, 141.7, 138.4, 137.2, 135.7, 135.4, 134.2, 132.8, 130.1, 129.9, 129.4, 128.9, 128.8, 128.7, 128.5, 127.9, 126.2, 126.1, 126.0, 121.5, 119.2, 116.8, 61.0, 53.8, 21.8, 21.8, 20.1; IR (neat) 3488, 1725, 798 cm−1; HRMS (EI-TOF) calcd for C36H29ClO4S 592.1475, found 592.1476. (E)-3-Methoxy-2-phenyl-1-(1-tosylpropan-2-ylidene)-1,2dihydrocyclobuta[b]naphthalene (2l): Colorless oil, 163 mg, 72% yield; 1H NMR (400 MHz, CDCl3) δ 8.14 (d, J = 8.0 Hz, 1H), 7.81 (d, J = 8.0 Hz, 1H), 7.77 (d, J = 8.0 Hz, 2H), 7.48−7.40 (m, 2H), 7.35 (d, J = 8.0 Hz, 3H), 7.27 (s, 1H), 7.25−7.18 (m, 2H), 7.09 (d, J = 7.0 Hz, 2H), 4.50 (s, 1H), 3.69 (d, J = 14.0 Hz, 1H), 3.59 (s, 3H), 3.44 (d, J = 14.0 Hz, 1H), 2.44 (s, 3H), 2.13 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 148.1, 146.0, 144.8, 143.4, 141.9, 136.2, 135.7, 129.9, 128.9, 128.6, 128.3, 128.0, 127.4, 126.7, 126.2, 125.1, 123.3, 122.6, 117.4, 111.8, 60.7, 57.7, 54.9, 21.7, 20.2; IR (neat) 3493, 1716, 773 cm−1; HRMS (EITOF) calcd for C29H26O3S 454.1603, found 454.1601. (E)-1-(1-(4-Chlorophenylsulfonyl)propan-2-ylidene)-3-methoxy2-phenyl-1,2-dihydrocyclobuta[b]naphthalene (2m): Colorless oil, 178 mg, 75% yield; 1H NMR (400 MHz, CDCl3) δ 8.15 (d, J = 8.0 Hz, 1H), 7.81 (m, 3H), 7.53 (d, J = 8.0 Hz, 2H), 7.48−7.41 (m, 2H), 7.37 (s, 1H), 7.29−7.26 (m, 1H), 7.24 (dd, J = 7.0, 3.0 Hz, 2H), 7.13−7.07 6207

DOI: 10.1021/acs.joc.7b00762 J. Org. Chem. 2017, 82, 6202−6209

Article

The Journal of Organic Chemistry (m, 2H), 4.62 (s, 1H), 3.70 (d, J = 14.0 Hz, 1H), 3.62 (s, 3H), 3.47 (d, J = 14.0 Hz, 1H), 2.13 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 148.3, 146.4, 143.2, 141.7, 140.7, 137.6, 135.7, 130.0, 129.6, 129.0, 128.3, 128.0, 127.5, 126.8, 126.3, 125.2, 123.1, 122.7, 116.8, 111.9, 60.7, 57.8, 55.1, 20.1; IR (neat) 3495, 1712, 778 cm−1; HRMS (EI-TOF) calcd for C28H23ClO3S 474.1056, found 474.1058. (E)-2-Phenyl-1-(1-tosylpropan-2-ylidene)-1,2-dihydrocyclobuta[b]anthracen-3-yl Acetate (4a): Light yellow powder, 205 mg, 77% yield, mp 87−88 °C; 1H NMR (400 MHz, CDCl3) δ 8.42 (d, J = 22.0 Hz, 2H), 7.99−7.94 (m, 2H), 7.76−7.71 (m, 3H), 7.49−7.45 (m, 2H), 7.36 (d, J = 8.0 Hz, 2H), 7.23 (m, 3H), 7.05−6.99 (m, 2H), 4.04 (s, 1H), 3.69 (d, J = 14.0 Hz, 1H), 3.54 (d, J = 14.0 Hz, 1H), 2.47 (s, 3H), 2.31 (s, 3H), 2.17 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 167.2, 145.5, 144.0, 141.3, 138.6, 137.4, 135.4, 133.7, 132.8, 131.5, 129.9, 128.8, 128.5, 128.3, 127.9, 127.7, 127.4, 127.3, 126.4, 125.9, 125.8, 120.1, 119.9, 116.5, 60.9, 54.6, 21.7, 20.6, 20.2; IR (neat) 3576, 1737, 786 cm−1; HRMS (EI-TOF) calcd for C34H28O4S 532.1708, found 532.1710. (E)-2-p-Tolyl-1-(1-tosylpropan-2-ylidene)-1,2-dihydrocyclobuta[b]anthracen-3-yl Acetate (4b): Light yellow powder, 221 mg, 81% yield, mp 90−91 °C; 1H NMR (400 MHz, CDCl3) δ 8.42 (d, J = 19.0 Hz, 2H), 8.01−7.92 (m, 2H), 7.73 (d, J = 8.0 Hz, 3H), 7.51−7.43 (m, 2H), 7.36 (d, J = 8.0 Hz, 2H), 7.05 (d, J = 8.0 Hz, 2H), 6.90 (d, J = 8.0 Hz, 2H), 3.99 (s, 1H), 3.73 (d, J = 14.0 Hz, 1H), 3.55 (d, J = 14.0 Hz, 1H), 2.47 (s, 3H), 2.31 (s, 6H), 2.19 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 167.2, 145.5, 144.2, 141.3, 137.3, 136.9, 135.5, 133.7, 133.1, 131.5, 129.9, 129.4, 128.5, 128.3, 127.9, 127.5, 127.4, 126.4, 125.8, 125.7, 119.9, 119.8, 116.4, 60.9, 54.3, 21.7, 21.2, 20.6, 20.2; IR (neat) 3579, 1730, 784 cm−1; HRMS (EI-TOF) calcd for C35H30O4S 546.1865, found 546.1867. (E)-1-(1-(4-Chlorophenylsulfonyl)propan-2-ylidene)-2-p-tolyl-1,2dihydrocyclobuta[b]anthracen-3-yl Acetate (4c): Light yellow powder, 226 mg, 80% yield, mp 94−95 °C; 1H NMR (400 MHz, CDCl3) δ 8.43 (d, J = 16.0 Hz, 2H), 7.97 (m, 2H), 7.74 (d, J = 8.0 Hz, 3H), 7.53−7.45 (m, 4H), 7.06 (d, J = 8.0 Hz, 2H), 6.95 (d, J = 8.0 Hz, 2H), 4.39 (s, 1H), 3.77 (d, J = 14.0 Hz, 1H), 3.59 (d, J = 14.0 Hz, 1H), 2.32 (s, 3H), 2.28 (s, 3H), 2.20 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 167.3, 144.6, 141.2, 140.9, 137.5, 137.3, 137.0, 135.4, 133.7, 132.8, 131.5, 129.8, 129.6, 129.5, 128.3, 127.9, 127.6, 127.5, 126.4, 125.9, 125.8, 112.0, 119.2, 116.6, 60.8, 54.7, 21.2, 20.6, 20.1; IR (neat) 3589, 1736, 783 cm−1; HRMS (EI-TOF) calcd for C34H27ClO4S 566.1319, found 566.1318. (E)-2-(4-Chlorophenyl)-1-(1-tosylpropan-2-ylidene)-1,2-dihydrocyclobuta[b]anthracen-3-yl Acetate (4d): Light yellow powder, 204 mg, 72% yield, mp 94−95 °C; 1H NMR (400 MHz, CDCl3) δ 8.43 (d, J = 13.0 Hz, 2H), 7.98 (dd, J = 10.0, 5.0 Hz, 2H), 7.76−7.68 (m, 3H), 7.48 (dd, J = 7.0, 3.0 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 6.98 (d, J = 8.0 Hz, 2H), 4.16 (s, 1H), 3.64 (d, J = 14.0 Hz, 1H), 3.56 (d, J = 14.0 Hz, 1H), 2.46 (s, 3H), 2.29 (s, 3H), 2.21 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 167.2, 145.5, 143.7, 141.1, 137.4, 137.3, 135.5, 133.7, 133.0, 132.2, 131.6, 131.5, 129.9, 129.1, 128.9, 128.4, 128.3, 127.9, 127.5, 126.3, 126.0, 125.9, 120.2, 120.0, 116.6, 60.9, 54.1, 21.7, 20.7, 20.2; IR (neat) 3576, 1746, 792 cm−1; HRMS (EI-TOF) calcd for C34H27ClO4S 566.1319, found 566.1320. (E)-2-(4-Chlorophenyl)-1-(1-(4-chlorophenylsulfonyl)propan-2ylidene)-1,2-dihydrocyclobuta[b]anthracen-3-yl Acetate (4e): Light yellow powder, 205 mg, 70% yield, mp 102−103 °C; 1H NMR (400 MHz, CDCl3) δ 8.49−8.41 (m, 2H), 8.00−7.95 (m, 2H), 7.78−7.71 (m, 3H), 7.54−7.47 (m, 4H), 7.23 (d, J = 8.0 Hz, 2H), 7.06−7.00 (m, 2H), 4.56 (s, 1H), 3.71−3.67 (d, J = 14.0 Hz, 1H), 3.59 (d, J = 14.0 Hz, 1H), 2.26 (s, 3H), 2.22 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 167.3, 144.1, 141.0, 140.9, 137.6, 137.4, 137.2, 133.6, 133.1, 131.9, 131.6, 129.7, 129.6, 129.2, 129.0, 128.3, 127.9, 127.6, 126.3, 126.1, 125.9, 120.1, 119.5, 116.8, 60.9, 54.5, 20.7, 20.2; IR (neat) 3576, 1725, 796 cm−1; HRMS (EI-TOF) calcd for C33H24Cl2O4S 586.0772, found 586.0774.

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1 H and 13C{1H} NMR spectra of all new compounds and crystal structure and data of 2a (PDF)

AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. ORCID

Hongwei Zhou: 0000-0001-8308-960X Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the Zhejiang Provincial Natural Science Foundation of China (No. LY14B020008) and Summit Program of Jiaxing University for Leading Talents.

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REFERENCES

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.7b00762. 6208

DOI: 10.1021/acs.joc.7b00762 J. Org. Chem. 2017, 82, 6202−6209

Article

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DOI: 10.1021/acs.joc.7b00762 J. Org. Chem. 2017, 82, 6202−6209