HETEROCYCLES

Paper | Special issue | Vol. 90, No. 1, 2015, pp. 271-297
Received, 5th March, 2014, Accepted, 19th May, 2014, Published online, 28th May, 2014.
DOI: 10.3987/COM-14-S(K)18

■ Copper Mediated Formation of Carbon-Heteroatom Bonds Using Organoboron Reagents and Ultrasound

Bryan J. Musolino and George W. Kabalka*

Chemistry Department, University of Tennessee, Knoxville, Tennessee, 37996-1600, U.S.A.

Abstract

This report summarizes research efforts focused on copper acetate mediated reactions to form new carbon-heteroatom bonds using organoboron reagents under ultrasound irradiation. The method involves the application of ultrasound irradiation to the Chan-Evans-Lam reaction to achieve O-arylation of phenols, N-arylation of anilines and indoles, and S-arylation of thiols. Ultrasound irradiation was found to decrease reaction times from 72 hours to 4 hours while improving the product yields an average of 20%.1 Representative C-O, C-N, and C-S coupling reactions were successfully scaled-up from the milligram to gram levels while maintaining good product yields offering potential applications in industrial processes.

INTRODUCTION
Over the past century, there have been numerous methods developed to achieve aryl-aryl coupling reactions under a variety of conditions while employing a variety of catalysts. However, the corresponding reactions involving the N-arylation, O-arylation, and S-arylation have not been investigated as fully; especially reactions involving thermally sensitive compounds that are of importance to the pharmaceutical industry.2 In 1998, the Chan-Lam reaction was developed for the C-N coupling reaction; it employs mild reaction conditions. The coupling reaction was then expanded to include the formation of C-S and C-O bonds and is now known as the Chan-Evans-Lam reaction.3 Unlike earlier syntheses that employed expensive or toxic metal catalysts, the Chan-Evans-Lam reaction uses a copper(II) acetate salts, under anhydrous conditions, to perform coupling reactions. The relatively mild conditions have allowed its application in a variety of syntheses that could not have been accomplished using previously reported procedures.2a,4 The primary downsides to the Chan-Evans-Lam reaction are time, typically 24-72 hours, and the requirement that anhydrous reaction conditions be employed.1c
We recently reported the use of copper(II) acetate, in the presence of ultrasonic radiation, for the homocoupling of several aryltrifluoroborate compounds.5 We then investigate the possibility of coupling various arylborates to phenols, anilines, indoles, and thiols. Herein, we report the results of our investigation which has led to successful coupling of phenols, anilines, indoles, and thiols with organoboron reagents while decreasing reaction times, increasing product yields, and eliminating the requirement the need for anhydrous reaction conditions.

RESULTS AND DISCUSSION
Survey experiments were conducted using naphthylboronic acid and phenol to determine the most effective reaction conditions. The first series of experiments employed one equivalent of phenol and 1.5 equivalents of naphthylboronic acid in DCM in the presence of 5.0 equivalents of triethylamine, and 4 equivalents of copper(II) acetate under ultrasound irradiation for six hours. Since the heat generated by the ultrasound is sufficiently high to evaporate DCM, the reaction vessel was placed in an ice/water bath maintained at 0-5 °C. A control experiment was carried out using identical conditions while stirring at room temperature for periods of 6 to 72 hours in the absence of ultrasound irradiation. The ultrasound experiment produced a product yield of 94%, the 6 hour control produced a yield of 23%, and the 72 hour control resulted in a yield of 72%. Subsequent experiments were conducted in which the ultrasound irradiation time was reduced to 4 hours, and the quantity of copper(II) acetate was decreased from 4 equivalents to 1 equivalent. The product yield was found to be essentially the same. It is possible that the cooling of the ice bath has a beneficial effect on the reaction: with a cooler solvent system the ultrasound probe is able to more easily shed built up internal heat, and thus improve the heat transfer from the probe to the surrounding media.6
The new method was evaluated employing various arylboronic acids with a variety of substituted phenols, anilines, indoles, and thiols. Arylboronic acids and the heteroatom aryls were chosen to include electron donating groups, electron withdrawing groups, and sterically hindered groups. The results are summarized in the Tables 1 - 3.

The syntheses of 2-phenoxynaphthalene, N-phenylnaphthalen-2-amine, and naphthalen-2-yl(phenyl)sulfane were repeated using a tenfold increase in the amount of all reagents and solvent. Sonication energy was increased to 20% amplitude (110 watts), sonication time increased to 8 hours (1 minute sonication pulse with a 3 second break), and the reaction vessel was changed to a 100 mL beaker. The external temperature was maintained at 0-5 °C. The yield was 80% using 2-phenoxynaphthalene, 78% using N-phenylnaphthalen-2-amine, and 87% using naphthalen-2-yl(phenyl)sulfane, indicating that the reactions are scalable to industrial standards. In an attempt to evaluate the electronic effects of the substituent groups on the reaction, the yields were plotted against the reported sigma values, Table 4 through Table 6:

CONCLUSION
The use of ultrasound enhances the Chan-Lam-Evans modified Ullmann reaction. The reaction times are dramatically decreased from 72 hours to 4 hours with improvement in product yields. The method was successfully scaled-up from millimole to gram scale while maintaining good product yields. The new coupling methodology can be characterized as atom efficient, scalable, environmentally friendly, inexpensive, and capable of rapidly producing high yields of products.

EXPERIMENTAL
Representative Procedure for the Synthesis of 2-phenoxynaphthalene
Naphthylboronic acid (0.25 g, 1.5 mmol) was added with 0.094 g of phenol (1.0 mmol) to 15 mL of DCM. Copper(II) acetate (0.36 g, 2.0 mmol) was then added along with triethylamine (0.5g, 5.0 mmol), and the dismembrator horn placed in the reaction vessel. The sonicator was set to 55 watts and the reaction was allowed to proceed for 4 hours (1 minute pulse with a 3 second rest). Post reaction, the product was isolated by column chromatography. Product yields were determined by weight and purity was confirmed by GC/MS and NMR.
Characterization of Compounds
1H NMR and 13C NMR spectra were recorded either at 250 and 63 MHz or 300 and 75 MHz respectively. Chemical shifts for 1H NMR and 13C NMR spectra were referenced to TMS and the d-chloroform solvent shift. High quality mass spectrometry was carried out using a Qstar electron spray ionization mass spectrometer, in either positive (M+1) or negative mode (M-1), ionization energy of ±5000 e/v, injection rate of 20 μL/min.
2-Phenoxynaphthalene7: 1H NMR (300 MHz, CDCl3) δ 7.83 - 7.80 (m, 2H), 7.69 (d, J = 8.4 Hz, 1H), 7.44 - 7.31 (m, 6H), 7.16 - 7.01 (m, 3H). 13C NMR (75 MHz, CDCl3) δ 157.4, 154.4, 134.3, 130.6, 129.5, 127.8, 126.7, 126.4, 125.2, 123.0, 119.2, 116.9, 108.1. Anal. Calcd for C16H12O: 220.0888. Found: 221.1001 (M+1). GC RT 6.78 minutes.
2-(2,6-Dimethylphenoxy)naphthalene8: 1H NMR (300 MHz, CDCl3) δ 7.90 – 7.82 (m, 3H), 7.53 – 7.49 (m, 3H), 7.23 – 7.13 (m, 2H), 7.03 (d, J = 7.3 Hz, 2H), 2.32 (s, 6H). 13C NMR (75 MHz, CDCl3) δ 154.6, 151.2, 133.3, 129.0, 128.5, 126.7, 126.3, 125.7, 125.1, 123.8, 123.2, 114.4, 108.0, 16.8. Anal. Calcd for C18H16O: 248.1201 Found: 249.1113 (M+1). GC RT 7.48 minutes.
4-(Naphthalen-2-yloxy)benzonitrile9: 1H NMR (300 MHz, CDCl3) δ 7.95 – 7.83 (m, 5H), 7.66 – 7.49 (m, 3H), 7.39 (s, 1H), 7.08 (d, J = 8.7 Hz, 2H).
13C NMR (63 MHz, D2O) δ 161.9, 153.9, 133.8, 132.9, 130.1, 129.2, 127.4, 125.4, 122.9, 119.5, 117.6, 116.5, 109.2, 104.6. Anal. Calcd for C17H11NO: 245.0841. Found: 244.0900 (M-1). GC RT 18.05 minutes.
2-(4-Nitrophenoxy)naphthalene10: 1H NMR (300 MHz, CDCl3) δ 8.24 – 8.20 (m, 2H), 7.93 – 7.85 (m, 3H), 7.55 – 7.51 (m, 4H), 7.29 – 7.21 (m, 2H). 13C NMR (63 MHz, D2O) δ 162.5, 152.8, 141.9, 135.8, 130.2, 129.7, 127.8, 126.0, 125.8, 124.4, 123.7, 117.4, 116.2, 108.4. Anal. Calcd for C16H11NO3: 265.0739. Found: 264.0811 (M-1). GC RT 20.18 minutes.
2-(3-Methoxyphenoxy)naphthalene10: 1H NMR (300 MHz, CDCl3) δ 7.90 – 7.83 (m, 3H), 7.54 – 7.45 (m, 3H), 7.37 (t, J = 6.7 Hz, 1H), 7.09 (d, J = 8.3 Hz, 1H), 6.86 – 6.75 (m, 3H), 3.81 (s, 3H).
13C NMR (63 MHz, D2O) δ 161.2, 158.6, 155.0, 134.5, 130.4, 130.2, 129.9, 127.8, 127.2, 126.6, 124.8, 120.1, 114.5, 111.3, 109.3, 105.2, 55.4. Anal. Calcd for C17H14O2: 250.0994 Found: 249.1002 (M-1). GC RT 15.11 minutes.
2-(4-Iodophenoxy)naphthalene11: 1H NMR (300 MHz, CDCl3) δ 7.90 – 7.84 (m, 3H), 7.73 (d, J = 8.2 Hz, 2H), 7.55 – 7.44 (m, 3H), 6.85 (d, J = 8.4 Hz, 1H), 6.66 (d, J = 8.4 Hz, 2H). 13C NMR (63 MHz, D2O) δ 156.7, 154.5, 138.1, 133.2, 129.9, 127.7, 127.0, 126.5, 125.7, 118.2, 114.4, 108.8, 81.2. Anal. Calcd for C16H11IO: 345.9855. Found: 345.0005 (M-1). GC RT 19.38 minutes.
2-(4-Bromophenoxy)naphthalene11: 1H NMR (300 MHz, CDCl3) δ 7.94 – 7.89 (m, 3H), 7.61 (d, J = 8.7 Hz, 2H), 7.51 (d, J = 8.9 Hz, 1H), 7.47 – 7.35 (m, 4H), 7.05 (d J = 7.8 Hz, 1H). 13 CNMR (63 MHz, D2O): δ 156.4, 154.5, 133.4, 132.7, 130.3, 130.1, 128.0, 127.1, 126.6, 124.9, 119.8, 117.5, 144.4, 109.5. Anal. Calcd for C16H11BrO: 297.9993. Found: 297.0011 (M-1). GC RT 17.36 minutes.
2-(Naphthalen-2-yloxy)isoindoline-1,3-dione12: 1H NMR (300 MHz, CDCl3) δ 7.96 – 7.89 (m, 6H), 7.55 (d, J = 8.0 Hz, 1H), 7.41 – 7.35 (m, 3H), 7.10 (d, J = 7.5 Hz, 1H). 13C NMR (63 MHz, D2O) δ 161.3, 150.7, 137.7, 133.4, 129.1, 128.5, 127.8, 127.1, 126.3, 125.6, 122.5, 121.6, 110.6, 104.9. Anal. Calcd for C18H11NO3: 289.0739. Found: 288.0814 (M-1). GC RT 18.73 minutes.
1-Phenoxy-4-(trifluoromethyl)benzene13: 1H NMR (300 MHz, CDCl3) δ 7.60 (d, J = 8.4 Hz, 2H), 7.40 (t, J = 7.5 Hz, 2H), 7.24 (t, J =7.5 Hz, 1H), 7.10 – 7.05 (m, 4H). 13C NMR (63 MHz, D2O) δ 161.2, 158.8, 128.6, 126.8, 124.1, 119.7, 118.8, 116.5. Anal. Calcd for C13H9F3O: 238.0605 Found: 237.0717 (M-1). GC RT 7.48 minutes.
1,3-Dimethyl-2-(4-(trifluoromethyl)phenoxy)benzene4: 1H NMR (250 MHz, D2O oxide) δ 7.59 (d, J = 8.3 Hz, 2H), 7.21 (d, J = 6.4 Hz, 2H), 7.06 (t, J = 7.5 Hz, 1H), 6.98 (d, J = 7.4 Hz, 2H), 2.32 (s, 6H). 13C NMR (63 MHz, D2O) δ 165.0, 152.0, 128.5, 127.1, 126.1, 125.5, 123.0, 120.1, 15.6. Anal. Calcd for C15H13F3O: 266.0918. Found: 265.1101 (M-1). GC RT 7.88 minutes.
4-(4-(Trifluoromethyl)phenoxy)benzonitrile13: 1H NMR (300 MHz, CDCl3) δ 7.53 (d, J = 8.4 Hz, 2H), 7.41 (d, J = 8.7 Hz, 2H), 7.26 – 7.19 (m, 4H).13C NMR (63 MHz, D2O) δ 161.2, 158.8, 128.6, 126.8, 124.1, 119.7, 118.8, 116.5. Anal. Calcd for C14H8F3NO: 263.0558. Found: 262.0722 (M-1). GC RT 12.87 minutes.
1-Bromo-4-(4-(trifluoromethyl)phenoxy)benzene14: 1H NMR (300 MHz, CDCl3) δ 7.83 (d, J = 8.0 Hz, 2H), 7.47 – 7.41 (m, 4H), 6.99 (d, J = 8.1 Hz, 2H). 13C NMR (75 MHz, CDCl3) δ 146.2, 157.6, 132.3, 127.1, 125.8, 123.4, 119.9, 117.8. Anal. Calcd for C13H8BrF3O: 315.9711. Found: 315.0002 (M-1). GC RT 10.00 minutes.
1-(4-Phenoxyphenyl)ethanone13: 1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.5 Hz, 2H), 7.37 – 7.41 (m, 2H), 7.18 – 7.21 (m, 1H), 7.08 (d, J = 8.5 Hz, 2H), 7.01 (d, J = 8.5 Hz, 2H), 2.57 (s, 3H). 13C NMR (63 MHz, D2O) δ 198.2, 160.7, 159.1, 128.3, 128.0, 122.7, 119.0, 116.1, 26.3. Anal. Calcd for C14H12O2: 212.0837. Found: 211.0901 (M-1). GC RT 9.90 minutes.
1-(4-(2,6-Dimethylphenoxy)phenyl)ethanone15: 1H NMR (250 MHz, D2O) δ 8.10 (d, J = 7.0 Hz, 2H), 7.26 – 7.21 (m, 3H), 7.06 (d, J = 7.8 Hz, 2H), 2.26 (s, 3H), 2.16 (s, 6H). 13C NMR (63 MHz, D2O) δ 192.5, 164.0, 152.2, 133.0, 130.7, 128.3, 126.8, 125.8, 123.2, 119.8, 26.3, 15.8. Anal. Calcd for C16H16O2: 240.1150. Found: 239.1200 (M-1). GC RT 8.91 minutes.
4-(4-Acetylphenoxy)benzonitrile16: 1H NMR (300 MHz, CDCl3) δ 8.12 (d, J = 8.3 Hz, 2H), 7.85 (d, J = 8.9 Hz, 2H), 7.23 (m, 4H), 2.54 (s, 3H). 13C NMR (63 MHz, D2O) δ 198.6, 160.7, 133.8, 130.6, 128.0, 119.0, 116.4, 102.1, 26.3. Anal. Calcd for C15H11NO2: 237.0790. Found: 236.0881 (M-1). GC RT 9.12 minutes.
1-(4-(4-Bromophenoxy)phenyl)ethanone15: 1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.5 Hz, 2H), 7.53 (d, J = 8.7 Hz, 2H), 6.96 – 6.90 (m, 4H), 2.63 (s, 3H). 13C NMR (63 MHz, D2O) δ 198.5, 161.7, 155.1, 132.2, 130.8, 128.4, 117.2, 116.5, 115.2, 26.5. Anal. Calcd for C14H11BrO2: 289.9942. Found: 289.0007 (M-1). GC RT 13.61 minutes.
3-Phenoxyphenol16: 1HNMR (300 MHz, CDCl3) δ 9.88 (s, 1H), 7.40 – 7.31 (m, 2H), 7.25 – 7.14 (m, 4H), 6.94 (d, J = 7.4, 1H), 6.50 – 6.46 (m, 2H). 13CNMR (63 MHz, D2O) δ 158.6, 155.4, 130.4, 129.6, 123.5, 120.7, 110.8, 107.4, 106.0. Anal. Calcd for C12H10O2: 186.0681. Found: 187.0555 (M+1). GC RT 7.75 minutes.
3-(2,6-Dimethylphenoxy)phenol17: 1H NMR (300 MHz, CDCl3) δ 9.85 (s, 1H), 7.29 – 7.11 (m, 2H), 7.06 (d, J = 5.5 Hz, 2H), 6.93 (d, J = 7.4 Hz, 1H), 6.82 – 6.74 (m, 2H), 2.14 (s, 6H). 13C NMR (63 MHz, D2O) δ 156.1, 154.5, 151.1, 132.3, 131.2, 129.3, 128.3, 115.1, 114.2, 108.8, 16.5. Anal. Calcd for C14H14O2: 214.0994. Found: 215.0887 (M+1). GC RT 6.97 minutes.
4-(3-Hydroxyphenoxy)benzonitrile18: 1H NMR (300 MHz, CDCl3) δ 9.90 (s, 1H), 7.87 (d, J = 8.1 Hz, 2H), 7.47 – 7.17 (m, 3H), 7.04 – 6.92 (m, 3H). 13C NMR (63 MHz, D2O) δ 164.4, 159.7, 155.5, 134.0, 129.3, 119.4, 117.5, 110.5, 108.8, 104.0, 103.3. Anal. Calcd for C13H9NO2: 211.0633. Found: 212.0506 (M+1). GC RT 7.77 minutes.
3-(4-Bromophenoxy)phenol19: 1H NMR (300 MHz, CDCl3) δ 9.75 (s, 1H), 7.75 (d, J = 8.9 Hz, 2H), 7.47 (d, J = 8.7 Hz, 2H), 7.26 – 7.20 (m, 1H), 7.05 – 6.98 (m, 1H), 6.49 (m, 208H). 13C NMR (63 MHz, D2O) δ 156.3, 155.6, 155.1, 132.3, 129.6, 120.5, 117.2, 115.3, 112.3, 104.9. Anal. Calcd for C12H9BrO2: 263.9786. Found: 262.9523 (M-1). GC RT 8.59 minutes.
N,N-Dimethyl-3-phenoxyaniline20: 1H NMR (300 MHz, CDCl3) δ 7.27 – 7.23 (m, 2H), 7.16 – 7.12 (m, 1H), 6.83 (d, J = 7.8 Hz, 3H), 6.78 – 6.74 (m, 2H), 6.74 (d, J = 7.4 Hz, 1H), 2.90 (s, 6H). 13C NMR (63 MHz, D2O) δ 157.9, 156.6, 148.6, 129.9, 129.6, 122.8, 119.7, 107.9, 107.1, 103.7, 40.8. Anal. Calcd for C14H15NO: 213.1154. Found: 214.1010 (M+1). GC RT 8.41 minutes.
4-(3-(Dimethylamino)phenoxy)benzonitrile18: 1H NMR (250 MHz, D2O) δ 7.83 – 7.80 (m, 2H), 7.32 – 7.21 (m, 2H), 6.81 – 6.75 (m, 1H), 6.74 – 6.71 (m, 2H), 6.40 (d, J = 7.1 Hz, 1H), 3.11 (s, 6H). 13C NMR (63 MHz, D2O) δ 160.5, 158.2, 151.7, 133.7, 128.6, 117.2, 116.0, 108.8, 107.4, 106.3, 102.1, 40.4. Anal. Calcd for C15H14N2O: 238.1106. Found: 237.1212 (M-1). GC RT 7.01 minutes.
1-Methyl-4-phenoxybenzene7: 1H NMR (250 MHz, D2O) δ 7.35 - 7.30 (m, 2H), 7.15 – 7.11 (m, 2H), 7.08 – 7.04 (m, 1H), 6.97 – 6.92 (m, 2H), 6.90 – 6.88 (m, 2H), 2.30 (s, 3H). 13C NMR (63 MHz, D2O) δ 158.5, 155.7, 133.3, 129.6, 120.5, 118.2, 115.3, 21.2. Anal. Calcd for C13H12O: 184.0888. Found: 185.0759 (M+1). GC RT 8.41 minutes.
1,3-Dimethyl-2-(p-tolyloxy)benzene21: 1H NMR (300 MHz, CDCl3) δ 7.29 – 7.00 (m, 3H), 6.81 (d, J = 7.2 Hz, 2H), 6.55 (d, J = 7.9 Hz, 2H), 2.32 (s, 3H), 2.07 (s, 6H). 13C NMR (63 MHz, D2O) δ 154.5, 151.6, 132.5, 129.9, 128.8, 128.1, 124.8, 114.2, 22.9, 16.7. Anal. Calcd for C15H16O: 212.1201. Found: 213.1108 (M+1). GC RT 9.42 minutes.
4-(p-Tolyloxy)benzonitrile13: 1H NMR (300 MHz, CDCl3) δ 7.53 (d, J = 8.7 Hz, 2H), 7.24 – 7.11 (m, 2H), 6.81 (d, J = 6.4 Hz, 4H), 2.33 (s, 3H). 13C NMR (63 MHz, D2O) δ 166.9, 155.4, 133.9, 133.9, 130.5, 120.2, 118.8, 117.4, 104.8, 21.4. Anal. Calcd for C14H11NO: 209.0841. Found: 208.0735 (M-1). GC RT 14.67 minutes.
1-Bromo-4-(p-tolyloxy)benzene22: 1H NMR (300 MHz, CDCl3) δ 7.73 (d, J = 8.7 Hz, 2H), 7.46 (d, J = 8.5 Hz, 2H), 6.96 (d, J = 8.8 Hz, 2H), 6.88 (d, J = 8.6 Hz, 2H), 2.35 (s, 3H). 13C NMR (63 MHz, D2O) δ 157.0, 154.4, 133.5, 132.5, 130.4,119.8, 119.2, 117.2, 115.1, 20.7. Anal. Calcd for C13H11BrO: 261.9993. Found: 261.0056 (M-1). GC RT 16.36 minutes.
N-Methyl-N-phenylnaphthalen-2-amine23: 1H NMR (300 MHz, CDCl3) δ 7.82 – 7.76 (m, 2H), 7.66 – 7.50 (m, 4H), 7.45 (t, J = 6.3 Hz, 2H), 7.29 – 7.21 (m, 2H), 6.96 (d, J = 7.7 Hz, 2H), 3.38 (s, 3H). 13C NMR (63 MHz, D2O) δ 149.9, 143.6, 136.8, 129.0, 128.3, 127.4, 127.3, 127.0, 125.7, 118.2, 116.0, 106.0, 45.2. Anal. Calcd for C17H15N: 233.1204. Found: 234.0997 (M+1). GC RT 15.76 minutes.
N-Phenylnaphthalen-2-amine23: 1H NMR (300 MHz, CDCl3) δ 7.86 – 7.78 (m, 2H), 7.72 (d, J = 7.9 Hz, 1H), 7.61 – 7.55 (m, 5H), 7.44 – 7.35 (m, 4H), 4.41 (s, 1H). 13C NMR (63 MHz, D2O) δ 142.7, 133.1, 129.1, 128.8, 127.6, 126.2, 125.6, 123.1, 120.9, 111.0. Anal. Calcd for C16H13N: 219.1048. Found: 220.0879 (M+1). GC RT 16.50 minutes.
N-(4-Chlorophenyl)naphthalen-2-amine24: 1H NMR (300 MHz, CDCl3) δ 7.94 – 7.63 (m, 4H), 7.50 – 7.41 (m, 4H), 7.34 – 7.30 (m, 2H), 7.25 – 7.22 (m, 1H), 3.69 (s, 1H). 13C NMR (75 MHz, CDCl3) δ 144.9, 141.4, 133.2, 128.8, 127.6, 126.3, 125.6, 123.4, 122.5, 118.9, 115.9, 111.6. Anal. Calcd for C16H12ClN: 253.0658. Found: 252.0944 (M-1). GC RT 20.17 minutes.
2-(Naphthalen-2-yl)isoindoline: 1H NMR (300 MHz, CDCl3) δ 7.87 – 7.63 (m, 4H), 7.41 – 7.34 (m, 6H), 7.02 (s, 1H), 4.57 (s, 4H). 13C NMR (75 MHz, CDCl3) δ 144.9, 137.7, 135.2, 129.1, 127.8, 125.5, 121.6, 115.1, 105.0, 53.8. Anal. Calcd for C18H15N: 245.1204. Found: 256.1310 (M+1). GC RT 22.56 minutes.
N-Methyl-N-(4-nitrophenyl)naphthalen-2-amine: 1H NMR (300 MHz, CDCl3) δ 8.07 (d, J = 9.2 Hz, 2H), 7.84 – 7.77 (m, 2H), 7.47 – 7.35 (m, 6H), 6.49 – 6.47 (m, 1H), 2.90 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 154.3, 143.5, 137.9, 133.5, 129.0, 127.9, 126.4, 125.9, 122.8, 120.3, 118.1, 110.7, 42.3. Anal. Calcd for C17H14N2O2: 278.1055. Found: 277.1112 (M-1). GC RT 11.60 minutes.
1-(Naphthalen-2-yl)-1H-benzo[d]imidazole25: 1H NMR (300 MHz, CDCl3) δ 8.58 – 8.54 (m, 1H), 8.00 – 7.89 (m, 3H), 7.80 (d, J = 8.7 Hz, 1H), 7.67 – 7.65 (m, 1H), 7.54 – 7.46 (m, 3H), 7.25 – 7.18 (m, 3H). 13C NMR (75 MHz, CDCl3) δ 143.0, 142.8, 134.2, 134.0, 133.8, 133.0, 132.8, 130.0, 129.1, 127.3, 122.9, 122.5, 121.7, 119.4, 110.7. Anal. Calcd for C17H12N2: 244.1000. Found: 245.1152 (M+1). GC RT 21.19 minutes.
N-(p-Tolyl)naphthalen-2-amine23: 1H NMR (300 MHz, CDCl3) δ 7.82 – 7.74 (m, 2H), 7.49 – 7.42 (m, 4H), 7.28 – 7.24 (m, 4H), 7.11 (s, 1H), 4.21 (s, 1H), 2.33 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 146.3, 140.1, 130.5, 129.6, 128.0, 125.1, 119.9, 118.6, 118.1, 116.6, 107.0, 20.4. Anal. Calcd for C17H15N: 233.1204. Found: 234.1178 (M+1). GC RT 14.96 minutes.
N-(4-Methoxyphenyl)-N-methylnaphthalen-2-amine23: 1H NMR (300 MHz, CDCl3) δ 7.87 - 7.70 (m, 2H), 7.51 - 7.27 (m, 4H), 7.18 – 7.10 (m, 3H), 6.88 (d, J = 7.7 Hz, 2H), 4.26 (s, 1H), 3.44 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 152.4, 144.7, 142.6, 133.5, 129.6, 127.9, 126.4, 125.9, 122.6, 120.1, 116.2, 114.6, 108.4, 55.9, 43.5. Anal. Calcd for C18H17NO: 263.1310. Found: 264.1078 (M+1). GC RT 19.83 minutes.
N-Methyl-N-phenyl-4-(trifluoromethyl)aniline26: 1H NMR (300 MHz, CDCl3) δ 7.32 (d, J = 1.1 Hz, 2H), 7.30 – 7.29 (m, 2H), 6.84 (t, J = 1.1 Hz, 1H), 6.72 – 6.70 (m, 4H), 3.15 (s, 1H). 13C NMR (75 MHz, CDCl3) δ 152.1, 149.2, 129.1, 125.5, 123.7, 121.6, 117.2, 112.4, 44.8. Anal. Calcd for C14H12F3N: 251.0922. Found: 250.1075 (M-1). GC RT 9.58 minutes.
N-Phenyl-4-(trifluoromethyl)aniline27: 1H NMR (250 MHz, D2O) δ 7.41 (d, J = 8.4 Hz, 2H), 7.29 (t, J = 7.5 Hz, 2H), 7.19 - 7.10 (m, 3H), 7.05 – 7.00 (m, 2H), 4.53 (s, 1H). 13C NMR (63 MHz, D2O) δ 147.6, 146.2, 128.9, 126.4, 122.5, 119.7, 118.2. Anal. Calcd for C13H10F3N: 237.0765. Found: 236.0908 (M-1). GC RT 12.69 minutes.
4-Chloro-N-(4-(trifluoromethyl)phenyl)aniline28: 1H NMR (300 MHz, CDCl3) δ 7.60 (d, J = 7.4 Hz, 2H), 7.40 (d, J = 7.3 Hz, 2H), 7.34 – 7.29 (m, 4H), 4.04 (s, 1H). 13C NMR (63 MHz, D2O) δ 144.5, 139.8, 129.5, 129.1, 128.6, 126.4, 122.7, 120.7. Anal. Calcd for C13H9ClF3N: 271.0376. Found: 270.0500 (M-1). GC RT 16.11 minutes.
N-Methyl-4-nitro-N-(4-(trifluoromethyl)phenyl)aniline: 1H NMR (250 MHz, D2O) δ 8.05 (d, J = 8.9 Hz, 2H), 7.75 – 7.61 (m, 4H), 7.30 – 7.09 (m, 2H), 3.62 (s, 1H). 13C NMR (63 MHz, D2O) δ 156.7, 147.2, 137.9, 133.5, 131.2, 125.9, 125.4, 119.4, 113.9, 43.4. Anal. Calcd for C14H11F3N2O2: 296.0773. Found: 295.0972 (M-1). GC RT 7.04 minutes.
4-Methyl-N-(4-(trifluoromethyl)phenyl)aniline26: 1H NMR (250 MHz, D2O) δ 7.46 – 7.21 (m, 8H), 4.12 (s, 1H), 2.31 (s, 3H). 13C NMR (63 MHz, D2O) δ 147.9, 138.8, 132.7, 129.9, 126.4, 123.3, 120.9, 20.9. Anal. Calcd for C14H12F3N: 251.0922. Found: 250.1122 (M-1). GC RT 13.53 minutes.
4-Methoxy-N-methyl-N-(4-(trifluoromethyl)phenyl)aniline29: 1H NMR (300 MHz, CDCl3) δ 7.23 (d, J = 8.9 Hz, 2H), 6.98 – 6.91 (m, 4H), 6.72 – 6.68 (m, 2H), 3.79 (s, 3H), 3.25 (s, 1H). 13C NMR (75 MHz, CDCl3) δ 153.5, 152.0, 143.6, 126.2, 125.3, 120.2, 116.2, 55.9, 42.0. Anal. Calcd for C15H14F3NO: 281.1027. Found: 280.1257 (M-1). GC RT 6.67 minutes.
1-(4-((4-Chlorophenyl)amino)phenyl)ethanone30: 1H NMR (250 MHz, D2O) δ 7.93 (d, J = 7.1 Hz, 2H), 7.54 – 7.40 (m, 4H), 7.25 (d, J = 8.9 Hz, 2H), 3.76 (s, 1H), 2.49 (s, 3H). 13C NMR (63 MHz, D2O) δ 198.2, 145.0, 141.0, 128.7, 128.3, 128.0, 122.3, 121.2, 115.9, 26.3. Anal. Calcd for C14H12ClNO: 245.0607. Found: 244.0779 (M-1). GC RT 7.79 minutes.
1-(4-(p-Tolylamino)phenyl)ethanone31: 1H NMR (300 MHz, CDCl3) δ 8.00 (d, J = 7.3 Hz, 2H), 7.54 – 7.51 (m, 2H), 7.34 – 7.30 (m, 4H), 3.36 (s, 1H), 2.63 (s, 3H), 2.32 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 196.4, 149.2, 137.9, 130.6, 129.7, 121.5, 113.8, 26.6, 20.3. Anal. Calcd for C15H15NO: 225.1154. Found: 226.0997 (M+1). GC RT 8.91 minutes.
1-(4-((4-Methoxyphenyl)(methyl)amino)phenyl)ethanone30: 1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.2 Hz, 2H), 7.59 – 7.40 (m, 4H), 6.55 (d, J = 8.0 Hz, 2H), 3.72 (s, 3H), 3.29 (s, 1H), 2.57 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 198.8, 153.0, 151.8, 140.8, 128.3, 128.0, 120.1, 120.0, 114.5, 55.4, 40.0, 26.2. Anal. Calcd for C16H17NO2: 255.1259. Found: 256.1119 (M+1). GC RT 6.57 minutes.
3-(Methyl(phenyl)amino)phenol32: 1H NMR (300 MHz, CDCl3) δ 9.51 (s, 1H), 7.19 – 7.12 (m, 2H), 6.82 – 6.79 (m, 3H), 6.73 – 6.65 (m, 4H), 4.15 (s, 1H). 13C NMR (75 MHz, CDCl3) δ 156.1, 149.1, 129.3, 129.0, 119.8, 117.1, 115.2, 112.3, 102.7, 46.2. Anal. Calcd for C13H13NO: 199.0997. Found: 198.1009 (M-1). GC RT 7.17 minutes.
3-(Phenylamino)phenol33: 1H NMR (300 MHz, CDCl3) δ 8.89 (s, 1H), 7.35 – 7.32 (m, 2H), 7.10 – 7.04 (m, 5H), 6.54 – 6.49 (m, 2H), 4.21 (s, 1H). 13C NMR (75 MHz, CDCl3) δ 157.8, 146.3, 143.8, 128.1, 127.8, 123.2, 122.0, 110.2, 109.1, 105.3. Anal. Calcd for C12H11NO: 185.0841. Found: 184.0994 (M-1). GC RT 6.62 minutes.
3-((4-Chlorophenyl)amino)phenol33: 1H NMR (300 MHz, CDCl3) δ 8.88 (s, 1H), 7.61 – 7.58 (m, 2H), 7.14 – 7.07 (m, 3H), 6.95 (t, J = 8.0 Hz, 1H), 6.62 – 6.58 (m, 2H), 4.78 (s, 1H). 13C NMR (75 MHz, CDCl3) δ 160.8, 148.8, 144.1, 129.3, 128.9, 124.8, 122.7, 109.4, 108.1, 104.4. Anal. Calcd for C12H10ClNO: 219.0451. Found: 218.0661 (M-1). GC RT 5.19 minutes.
N1,N1,N3-Trimethyl-N3-phenylbenzene-1,3-diamine34: 1H NMR (300 MHz, CDCl3) δ 7.23 – 7.17 (m, 4H), 6.72 – 6.66 (m, 4H), 6.46 (s, 1H), 3.32 (s, 3H), 2.95 (s, 6H). 13C NMR (75 MHz, CDCl3) δ 155.6, 150.2, 149.1, 129.6, 129.0, 120.0, 118.8, 107.0, 104.9, 41.3, 40.5. Anal. Calcd for C15H18N2: 226.1470. Found: 225.1001 (M-1). GC RT 7.92 minutes.
N1,N1-Dimethyl-N3-phenylbenzene-1,3-diamine34: 1H NMR (300 MHz, CDCl3) δ 7.38 – 7.35 (m, 2H), 7.09 – 7.00 (m, 5H), 6.88 – 6.84 (m, 1H), 6.48 (s, 1H), 4.10 (s, 1H), 2.93 (s, 6H). 13C NMR (75 MHz, CDCl3) δ 155.5, 143.8, 138.1, 129.7, 129.2, 120.4, 117.6, 112.6, 106.7, 106.0, 40.5. Anal. Calcd for C14H16N2: 212.1313. Found: 211.1219 (M-1). GC RT 9.51 minutes.
N1-(4-Chlorophenyl)-N3,N3-dimethylbenzene-1,3-diamine34: 1H NMR (300 MHz, CDCl3) δ 7.83 (d, J = 7.1 Hz, 2H), 7.45 (d, J = 6.6 Hz, 2H), 7.27 – 7.03 (m, 2H), 6.72 (d, J = 7.6 Hz, 1H), 6.43 (s, 1H), 4.11 (s, 1H), 2.89 (s, 6H). 13C NMR (75 MHz, CDCl3) δ 149.9, 141.3, 139.6, 128.6, 128.3, 127.7, 123.3, 111.9, 104.3, 39.8. Anal. Calcd for C14H15ClN2: 246.0924. Found: 245.1008 (M-1). GC RT 5.20 minutes.
N1,N1,N3-Trimethyl-N3-(4-nitrophenyl)benzene-1,3-diamine34: 1H NMR (300 MHz, CDCl3) δ 8.09 (d, J = 8.9 Hz, 2H), 7.49 – 7.40 (m, 2H), 7.14 (t, J = 8.8 Hz, 1H), 6.70 – 6.65 (m, 2H), 6.53 – 6.51 (m, 1H), 4.13 (s, 1H), 2.94 (s, 6H). 13C NMR (75 MHz, CDCl3) δ 158.3, 156.4, 147.6, 133.3, 129.0, 126.4, 120.1, 112.6, 105.0, 43.0, 40.6. Anal. Calcd for C15H17N3O2: 271.1321. Found: 270.1259 (M-1). GC RT 11.87 minutes.
N1,N1-Dimethyl-N3-(p-tolyl)benzene-1,3-diamine35: 1H NMR (300 MHz, CDCl3) δ 7.42 – 7.34 (m, 4H), 7.27 (t, J = 6.4 Hz, 1H), 7.18 – 7.06 (m, 1H), 7.06 – 6.97 (m, 1H), 6.78 – 6.76 (m, 1H), 4.14 (s, 1H), 2.97 (s, 6H), 2.35 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 151.3, 137.4, 129.8, 128.5, 120.6, 110.2, 105.0, 41.7, 21.1. Anal. Calcd for C15H18N2: 226.1470. Found: 225.1301 (M-1). GC RT 10.20 minutes.
N1-(4-Methoxyphenyl)-N1,N3,N3-trimethylbenzene-1,3-diamine: 1H NMR (300 MHz, CDCl3) δ 7.15 – 7.02 (m, 3H), 6.77 (d, J = 8.6 Hz, 2H), 6.73 – 6.68 (m, 2H), 6.26 – 6.23 (m, 1H), 4.05 (s, 1H), 3.75 (s, 3H), 2.90 (s, 6H). 13C NMR (75 MHz, CDCl3) δ 151.9, 151.9, 150.5, 142.5, 128.8, 121.1, 116.4, 105.9, 104.1, 55.6, 42.8, 40.3. Anal. Calcd for C16H20N2O: 256.1576. Found: 255.1431 (M-1). GC RT 12.42 minutes.
Methyl-phenyl-p-tolylamine23: 1H NMR (300 MHz, CDCl3) δ 7.26 – 7.17 (m, 7H), 6.88 – 6.81 (m, 2H), 4.88 (s, 1H), 2.68 (s, 6H). 13C NMR (75 MHz, CDCl3) δ 149.3, 148.2, 129.9, 129.2, 122.5, 117.2, 112.4, 45.3, 21.6. Anal. Calcd for C14H15N: 197.1204. Found: 196.1087 (M-1). GC RT 11.57 minutes.
4-Methyl-N-phenylaniline27: 1H NMR (300 MHz, CDCl3) δ 7.24 – 7.20 (m, 2H), 7.09 – 7.00 (m, 4H), 6.95 - 6.90 (m, 3H), 5.60 (s, 1H), 2.31 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 142.6, 138.6, 130.6, 129.2, 128.4, 122.6, 121.3, 118.9, 23.4. Anal. Calcd for C12H10ClNO: 219.0451. Found: 218.0661 (M-1). GC RT 5.19 minutes.
4-Chloro-N-(p-tolyl)aniline28: 1H NMR (250 MHz, D2O) δ 7.50 (d, J = 8.5 Hz, 2H), 7.29 (d, J = 7.3 Hz, 2H), 7.10 – 7.00 (m, 4H), 4.04 (s, 1H), 2.80 (s, 3H). 13C NMR (63 MHz, D2O) δ 144.1, 142.4, 129.9, 129.0, 126.6, 125.1, 119.9, 22.1. Anal. Calcd for C13H12ClN: 217.0658. Found: 216.0771 (M-1). GC RT 5.19 minutes.
di-p-Tolylamine28: 1H NMR (250 MHz, D2O) δ 7.29 (d, J = 7.9 Hz, 4H), 7.05 (d, J = 7.4 Hz, 4H), 5.52 (s, 1H), 2.52 (s, 6H). 13C NMR (63 MHz, D2O) δ 141.07, 130.04, 129.98, 129.40, 117.80, 20.51. Anal. Calcd for C14H15N: 197.1204. Found: 196.1107 (M-1). GC RT 14.46 minutes.
4-Methoxy-N-methyl-N-(p-tolyl)aniline31: 1H NMR (300 MHz, CDCl3) δ 7.12 – 7.04 (m, 6H), 6.79 (d, J = 8.8 Hz, 2H), 4.21 (s, 1H), 3.77 (s, 3H), 2.27 (s, 3H). 13C NMR (63 MHz, D2O) δ 155.25, 147.33, 142.59, 129.59, 129.24, 121.22, 120.49, 114.49, 55.42, 40.31, 20.63. Anal. Calcd for C15H17NO: 227.1310. Found: 226.1214 (M-1). GC RT 8.60 minutes.
Naphthalen-2-yl(phenyl)sulfane11: 1H NMR (300 MHz, CDCl3) δ 7.84 – 7.78 (m, 4H), 7.50 - 7.36 (m, 8H). 13C NMR (75 MHz, CDCl3) δ 134.9, 131.4, 127.2, 126.9, 125.8, 125.8, 125.4, 125.2, 125.1, 125.0, 123.8, 123.6. Anal. Calcd for C16H12S: 236.0660. Found: 235.0772 (M-1). GC RT 15.85 minutes.
Naphthalen-2-yl(4-nitrophenyl)sulfane36: 1H NMR (300 MHz, CDCl3) δ 7.85 – 7.65 (m, 5H), 7.52 – 7.44 (m, 3H), 7.38 – 7.25 (m, 3H). 13C NMR (75 MHz, CDCl3) δ 146.8, 141.9, 135.8, 135.0, 133.7, 130.2, 127.8, 126.3, 125.8, 125.6, 124.4. Anal. Calcd for C16H11NO2S: 281.0510. Found: 280.0447 (M-1). GC RT 9.05 minutes.
Naphthalen-2-yl(p-tolyl)sulfane37: 1H NMR (300 MHz, CDCl3) δ 7.87 – 7.69 (m, 3H), 7.62 (s, 1H), 7.55 – 7.37 (m, 5H), 7.17 (d, J = 8.0 Hz, 2H), 2.34 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 140.8, 135.7, 132.1, 131.7, 128.1, 126.8, 126.1, 124.1, 19.3. Anal. Calcd for C17H14S: 250.0816. Found: 249.0955 (M-1). GC RT 8.99 minutes.
(2,6-Dimethylphenyl)(naphthalen-2-yl)sulfane38: 1H NMR (300 MHz, CDCl3) δ 7.83 – 7.55 (m, 3H), 7.69 (s, 1H), 7.46 – 7.39 (m, 3H), 6.94 – 6.89 (m, 3H), 2.23 (s, 6H). 13C NMR (75 MHz, CDCl3) δ 143.4, 134.7, 133.4, 131.3, 130.8, 129.2, 128.0, 127.8, 127.2, 125.8, 21.4. Anal. Calcd for C18H16S: 264.0973. Found: 263.1107 (M-1). GC RT 8.78 minutes.
(4-Chlorophenyl)(naphthalen-2-yl)sulfane39: 1H NMR (300 MHz, CDCl3) δ 8.14 (d, J = 9.3 Hz, 1H), 7.83 – 7.74 (m, 5H), 7.38 – 7.31 (m, 3H), 7.26 (d, J = 8.4 Hz, 2H). 13C NMR (75 MHz, CDCl3) δ 135.9, 135.0, 133.6, 133.1, 131.7, 131.1, 129.3, 128.2, 127.8, 127.0, 126.5, 125.8. Anal. Calcd for C16H11ClS: 270.0270. Found: 269.0644 (M-1). GC RT 9.94 minutes.
Naphthalen-2-yl(4-(trifluoromethyl)phenyl)sulfane40: 1H NMR (300 MHz, CDCl3) δ 8.12 (d, J = 8.3 Hz, 1H), 7.91 – 7.87 (m, 3H), 7.82 – 7.68 (m, 5H), 7.32 (d, J = 8.0 Hz, 2H). 13C NMR (75 MHz, cdcl3) δ 140.8, 134.7, 133.4, 129.7, 127.8, 126.5, 125.8, 125.6, 123.3. Anal. Calcd for C17H11F3S: 304.0534. Found: 303.0728 (M-1). GC RT 11.26 minutes.
(4-Methoxyphenyl)(naphthalen-2-yl)sulfane37: 1H NMR (300 MHz, CDCl3) δ 7.85 – 7.70 (m, 3H), 7.65 (s, 1H), 7.55 – 7.52 (m, 3H), 7.38 (d, J = 8.0 Hz, 2H), 7.20 (d, J = 8.0 Hz, 2H), 3.87 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 159.6, 133.1, 132.2, 129.0, 128.0, 127.4, 125.4, 114.2, 54.8. Anal. Calcd for C17H14OS: 266.0765. Found: 265.1008 (M-1). GC RT 16.14 minutes.
(2-Methylbutyl)(naphthalen-2-yl)sulfane40: 1H NMR (300 MHz, CDCl3) δ 7.77 – 7.57 (m, 3H), 7.47 (s, 1H), 7.28 – 7.13 (m, 3H), 2.73 (dd, J = 12.7, 5.8 Hz, 2H), 2.04 – 1.89 (m, 1H), 1.79 – 1.66 (m, 2H), 1.56 – 1.42 (m, 6H). 13C NMR (75 MHz, CDCl3) δ 130.5, 129.7, 129.2, 128.3, 127.5, 126.0, 125.9, 44.8, 34.4, 28.4, 23.3, 11.2. Anal. Calcd for C15H18S: 230.1129. Found: 229.0918 (M-1). GC RT 12.99 minutes.
Naphthalen-2-yl(perfluorophenyl)sulfane40: 1H NMR (250 MHz, D2O) δ 7.82 (d, J = 8.4 Hz, 1H), 7.72 - 7.60 (m, 3H), 7.50 - 7.36 (m, 3H). 13C NMR (63 MHz, D2O) δ 150.0, 141.9, 138.4, 133.5, 129.7, 129.1, 128.6, 126.9, 126.7, 125.7, 100.3. Anal. Calcd for C16H7F5S: 326.0189. Found: 325.0344 (M-1). GC RT 15.64 minutes.
Phenyl(4-(trifluoromethyl)phenyl)sulfane41: 1H NMR (300 MHz, CDCl3) δ 7.53 – 7.41 (m, 7H), 7.22 – 7.18 (m, 2H). 13C NMR (75 MHz, CDCl3) δ 139.5, 137.0, 129.0, 127.5, 127.1, 126.7, 126.7, 124.6, 122.8. Anal. Calcd for C13H9F3S: 254.0377. Found: 253.0475 (M-1). GC RT 13.75 minutes.
(4-Nitrophenyl)(4-(trifluoromethyl)phenyl)sulfane41: 1H NMR (300 MHz, CDCl3) δ 8.01 (d, J = 8.7 Hz, 2H), 7.54 (d, J = 7.5 Hz, 2H), 7.47 (d, J = 8.4 Hz, 2H), 7.18 (d, J = 8.4 Hz, 2H). 13C NMR (75 MHz, CDCl3) δ 149.63, 141.64, 139.66, 132.68, 129.21, 126.08, 124.53, 123.95. Anal. Calcd for C13H8F3NO2S: 299.0228. Found: 298.0500 (M-1). GC RT 12.37 minutes.
p-Tolyl(4-(trifluoromethyl)phenyl)sulfane41: 1H NMR (300 MHz, CDCl3) δ 7.49 – 7.39 (m, 4H), 7.18 – 7.09 (m, 4H), 2.35 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 138.1, 137.4, 130.2, 129.7, 128.6, 123.3, 119.8, 20.9. Anal. Calcd for C14H11F3S: 268.0534. Found: 127.0784 (M-1). GC RT 12.11 minutes.
(4-Chlorophenyl)(4-(trifluoromethyl)phenyl)sulfane41: 1H NMR (300 MHz, CDCl3) δ 7.84 (d, J = 8.7 Hz, 2H), 7.48 (d, J = 7.5 Hz, 2H), 7.39 (d, J = 9.0 Hz, 2H), 7.29 (d, J = 8.4 Hz, 2H). 13C NMR (75 MHz, CDCl3) δ 143.0, 135.1, 133.6, 131.7, 131.1, 129.3, 127.8, 125.8. Anal. Calcd for C13H8ClF3S: 287.9987. Found: 287.0002 (M-1). GC RT 9.42 minutes.
(2-Methylbutyl)(4-(trifluoromethyl)phenyl)sulfane: 1H NMR (250 MHz, D2O) δ 7.35-7.29 (m, 4H), 2.75 (dd, J = 12.7, 5.8 Hz, 2H), 2.08 – 1.92 (m, 1H), 1.84 – 1.75 (m, 2H), 1.58 – 1.45 (m, 6H). 13C NMR (63 MHz, D2O) δ 142.5, 131.6, 128.5, 127.8, 125.8, 46.7, 34.5, 28.5, 18.6, 11.2. Anal. Calcd for C12H15F3S: 248.0847. Found: 247.0747 (M-1). GC RT 6.96 minutes.
(Perfluorophenyl)(4-(trifluoromethyl)phenyl)sulfane: 1H NMR (250 MHz, D2O) δ 7.50 (d, J = 8.2 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H). 13C NMR (63 MHz, D2O) δ 149.0, 141.0, 138.2, 135.9, 133.3, 132.4, 129.0, 126.3, 100.6. Anal. Calcd for C13H4F8S: 343.9906. Found: 343.0001 (M-1). GC RT 7.34 minutes.
1-(4-(Phenylthio)phenyl)ethanone37: 1H NMR (250 MHz, D2O) δ 7.91 (d, J = 5.8 Hz, 2H), 7.60 - 7.45 (m, 7H), 2.55 (s, 3H). 13C NMR (63 MHz, D2O) δ 197.5, 143.0, 134.6, 133.1, 128.8, 128.0, 127.8, 126.7, 26.1. Anal. Calcd for C14H12OS: 228.0609. Found: 227.0889 (M-1). GC RT 17.60 minutes.
1-(4-((4-Nitrophenyl)thio)phenyl)ethanone42: 1H NMR (300 MHz, CDCl3) δ 8.19 (d, J = 8.3 Hz, 2H), 7.96 (d, J = 7.4 Hz, 2H), 7.89 (d, J = 8.7 Hz, 2H), 7.61 (d, J = 8.6 Hz, 2H), 2.61 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 196.7, 146.9, 144.0, 141.9, 133.1, 129.5, 128.3, 124.4, 26.6. Anal. Calcd for C14H11NO3S: 273.0460. Found: 272.0551 (M-1). GC RT 12.50 minutes.
1-(4-(p-Tolylthio)phenyl)ethanone43: 1H NMR (250 MHz, D2O) δ 7.97 (d, J = 7.9 Hz, 2H), 7.26 – 7.20 (m, 4H), 6.78 (d, J = 8.4 Hz, 2H), 2.60 (s, 3H), 2.32 (s, 3H). 13C NMR (63 MHz, D2O) δ 193.0, 137.6, 134.1, 129.7, 129.7, 128.4, 128.4, 30.6, 20.9. Anal. Calcd for C15H14OS: 242.0765. Found: 241.0510 (M-1). GC RT 13.63 minutes.
1-(4-((2,6-Dimethylphenyl)thio)phenyl)ethanone44: 1H NMR (300 MHz, CDCl3) δ 7.96 – 7.90 (m, 2H), 7.52 – 7.42 (m, 4H), 7.10 – 7.04 (m, 1H), 2.60 (s, 3H), 2.23 (s, 6H). 13C NMR (75 MHz, CDCl3) δ 198.1, 143.3, 137.1, 134.7, 129.2, 128.5, 128.0, 127.6, 126.9, 77.4, 77.0, 76.6, 26.6, 21.4. Anal. Calcd for C16H16OS: 256.0922. Found: 255.1002 (M-1). GC RT 12.27 minutes.
1-(4-((4-Chlorophenyl)thio)phenyl)ethanone45: 1H NMR (300 MHz, CDCl3) δ 7.95 (d, J = 7.3 Hz, 2H), 7.43 – 7.38 (m, 4H), 6.82 (d, J = 8.4 Hz, 2H), 2.60 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 196.6, 144.0, 133.1, 132.6, 131.4, 129.9, 128.5, 128.3, 26.6. Anal. Calcd for C14H11ClOS: 262.0219. Found: 261.0442 (M-1). GC RT 9.46 minutes.
1-(4-((2-Methylbutyl)thio)phenyl)ethan-1-one: 1H NMR (250 MHz, D2O) δ 7.30-7.22 (m, 4H), 2.75 (dd, J = 12.5, 5.5 Hz, 2H), 2.45 (s, 3H), 2.06 – 1.92 (m, 1H), 1.79 – 1.66 (m, 2H), 1.55 – 1.40 (m, 6H). 13C NMR (63 MHz, D2O) δ 193.5, 137.1, 133.4, 130.4, 123.5, 46.7, 34.5, 28.5, 18.6, 11.2. Anal. Calcd for C13H18OS: 222.1078. Found: 221.0887 (M-1). GC RT 6.96 minutes.
3-((4-Nitrophenyl)thio)phenol46: 1H NMR (250 MHz, D2O) δ 8.90 (s, 1H), 8.15 (d, J = 8.6 Hz, 2H), 7.58 (d, J = 8.7 Hz, 2H), 6.85 – 6.79 (m, 3H), 6.72 (s, 1H). 13C NMR (63 MHz, D2O) δ 158.4, 144.0, 140.4, 137.0, 129.6, 124.4, 118.7, 115.2. Anal. Calcd for C12H9NO3S: 247.0303. Found: 246.0541 (M-1). GC RT 6.15 minutes.
3-(p-Tolylthio)phenol46: 1H NMR (250 MHz, D2O) δ 8.88 (s, 1H), 7.37 (d, J = 7.9 Hz, 2H), 7.13 – 7.07 (m, 4H), 6.93 – 6.65 (m, 2H), 2.29 (s, 3H). 13C NMR (63 MHz, D2O) δ 158.9, 140.4, 137.3, 133.8, 130.0, 129.7, 129.7, 128.4, 120.1, 115.24, 113.0, 20.9. Anal. Calcd for C13H12OS: 216.0609. Found: 215.0887 (M-1). GC RT 11.62 minutes.
3-((2,6-Dimethylphenyl)thio)phenol46: 1H NMR (300 MHz, CDCl3) δ 8.74 (s, 1H), 7.24 (d, J = 7.5 Hz, 2H), 7.18 – 6.97 (m, 1H), 6.94 – 6.89 (m, 2H), 6.85 (d, J = 7.7 Hz, 1H), 2.25 (s, 6H). 13C NMR (75 MHz, CDCl3) δ 155.5, 143.4, 134.7, 129.6, 129.3, 128.0, 123.1, 120.7, 115.2, 21.4. Anal. Calcd for C14H14OS: 230.0765. Found: 229.0455 (M-1). GC RT 12.45 minutes.
3-((4-Chlorophenyl)thio)phenol46: 1H NMR (250 MHz, D2O) δ 8.78 (s, 1H), 7.36 (d, J = 8.4 Hz, 2H), 7.23 (d, J = 8.4 Hz, 2H), 6.91 – 6.79 (m, 2H), 6.62 – 6.42 (m, 1H), 6.25 (s, 1H). 13C NMR (63 MHz, D2O) δ 158.7, 135.1, 133.6, 129.5, 129.3, 126.3, 119.9, 115.3. Anal. Calcd for C12H9ClOS: 236.0063. Found: 235.0150 (M-1). GC RT 9.48 minutes.
3-((2-Methylbutyl)thio)phenol47: 1H NMR (250 MHz, D2O) δ 8.89 (s, 1H), 7.28-6.83 (m, 4H), 2.70 (dd, J = 12.8, 6.0 Hz, 2H), 2.02 – 1.89 (m, 1H), 1.80 – 1.65 (m, 2H), 1.58 – 1.43 (m, 6H). 13C NMR (63 MHz, D2O) δ 158.1, 138.3, 129.5, 120.3, 116.3, 115.3, 46.6, 34.4, 28.4, 18.5, 11.2. Anal. Calcd for C11H16OS: 196.0922. Found: 195.0504 (M-1). GC RT 6.98 minutes.
N,N-Dimethyl-3-(phenylthio)aniline37: 1H NMR (300 MHz, CDCl3) δ 7.49 – 7.41 (m, 5H), 7.24 – 7.22 (m, 1H), 7.00 – 6.98 (m, 1H), 6.68 – 6.65 (m, 2H), 2.91 (s, 6H). 13C NMR (75 MHz, CDCl3) δ 151.0, 137.7, 137.0, 129.0, 127.5, 127.1, 121.2, 116.9, 112.6, 42.5. Anal. Calcd for C14H15NS: 229.0925. Found: 228.0645 (M-1). GC RT 14.67 minutes.
N,N-Dimethyl-3-((4-nitrophenyl)thio)aniline46: 1H NMR (300 MHz, CDCl3) δ 8.19 (d, J = 7.6 Hz, 2H), 7.62 (d, J = 7.6 Hz, 2H), 7.26 (s, 1H), 7.13 – 7.11 (m, 1H), 6.75 – 6.64 (m, 2H), 6.58 (d, J = 9.5 Hz, 2H), 2.94 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 151.7, 144.1, 141.3, 138.3, 131.4, 129.1, 124.5, 122.6, 118.0, 112.7, 40.6. Anal. Calcd for C14H14N2O2S: 274.0776. Found: 273.1141 (M-1). GC RT 6.02 minutes.
N,N-Dimethyl-3-(p-tolylthio)aniline: 1H NMR (250 MHz, D2O) δ 7.37 (d, J = 7.8 Hz, 2H), 7.30 (s, 1H), 7.21 – 7.18 (m, 2H), 7.08 – 7.06 (m, 1H), 6.95 – 6.67 (m, 2H), 3.08 (s, 6H), 2.29 (s, 3H). 13C NMR (63 MHz, D2O) δ 150.5, 141.7, 137.3, 133.8, 129.7, 129.0, 128.4, 122.7, 116.5, 112.6, 40.5, 21.0. Anal. Calcd for C15H17NS: 243.1082. Found: 242.0778 (M-1). GC RT 21.96 minutes.
3-((2,6-Dimethylphenyl)thio)-N,N-dimethylaniline: 1H NMR (300 MHz, CDCl3) δ 7.40 - 7.25 (m, 3H), 7.10-7.01 (m, 2H), 6.75-6.55 (m, 2H), 2.94 (s, 6H), 2.23 (s, 6H). 13C NMR (75 MHz, CDCl3) δ 150.6, 143.4, 138.6, 130.8, 129.2, 128.0, 127.0, 121.3, 116.6, 112.6, 40.6, 21.4. Anal. Calcd for C16H19NS: 257.1238. Found: 256.0998 (M-1). GC RT 9.78 minutes.
N,N-Dimethyl-3-((2-methylbutyl)thio)aniline: 1H NMR (300 MHz, CDCl3) δ 7.28 – 7.27 (m, 2H), 7.06 – 6.81 (m, 2H), 2.99 (s, 6H), 2.83 (dd, J = 13.4, 6.8 Hz, 2H), 2.14 – 2.00 (m, 1H), 1.84 – 1.77 (m, 2H), 1.64 – 1.57 (m, 6H). 13C NMR (75 MHz, CDCl3) δ 152.1, 138.4, 128.4, 116.2, 111.2, 109.8, 46.6, 40.9, 34.4, 28.4, 18.5, 11.1. Anal. Calcd for C13H21NS: 223.1395. Found: 222.1012 (M-1). GC RT 9.79 minutes.
Phenyl(p-tolyl)sulfane11: 1H NMR (250 MHz, D2O) δ 7.51 – 7.44 (m, 7H), 7.30 – 7.16 (m, 2H), 2.23 (s, 3H). 13C NMR (63 MHz, D2O) δ 140.4, 137.0, 129.0, 128.1, 127.5, 127.1, 23.3. Anal. Calcd for C13H12S: 200.0660. Found: 199.0881 (M-1). GC RT 13.49 minutes.
(4-Nitrophenyl)(p-tolyl)sulfane36: 1H NMR (300 MHz, CDCl3) δ 8.18 (d, J = 8.8 Hz, 2H), 7.80 (d, J = 8.8 Hz, 2H), 7.61 (d, J = 8.5 Hz, 2H), 7.55 (d, J = 8.5 Hz, 2H), 2.31 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 144.1, 140.2, 137.4, 132.3, 129.6, 127.9, 124.4, 21.5. Anal. Calcd for C13H11NO2S: 245.0510. Found: 244.0781 (M-1). GC RT 9.21 minutes.
di-p-Tolylsulfane48: 1H NMR (300 MHz, CDCl3) δ 7.40 (d, J = 8.1 Hz, 4H), 7.11 (d, J = 7.9 Hz, 4H), 2.33 (s, 6H). 13C NMR (63 MHz, D2O) δ 137.4, 130.5, 129.8, 128.5, 21.0. Anal. Calcd for C14H14S: 214.0816. Found: 213.0664 (M-1). GC RT 14.06 minutes.
(2,6-Dimethylphenyl)(p-tolyl)sulfane48: 1H NMR (300 MHz, CDCl3) δ 7.34 (d, J = 8.6 Hz, 2H), 7.18 – 6.97 (m, 5H), 2.25 (s, 9H). 13C NMR (75 MHz, CDCl3) δ 142.9, 139.0, 134.2, 129.5, 128.8, 128.3, 127.6, 127.3, 21.4, 21.0. Anal. Calcd for C15H16S: 228.0973. Found: 227.1221 (M-1). GC RT 5.26 minutes.
(4-Chlorophenyl)(p-tolyl)sulfane48: 1H NMR (250 MHz, D2O) δ 7.27 (d, J = 8.7 Hz, 2H), 7.23 (d, J = 8.8 Hz, 2H), 7.18 – 7.13 (m, 4H), 2.35 (s, 3H). 13C NMR (63 MHz, D2O) δ 140.6, 135.0, 133.5, 129.8, 129.2, 129.1, 20.4. Anal. Calcd for C13H11ClS: 234.0270. Found: 233.0478 (M-1). GC RT 5.26 minutes.
(2-Methylbutyl)(p-tolyl)sulfane48: 1H NMR (250 MHz, D2O) δ 7.22 (d, J = 7.8 Hz, 2H), 7.14 (d, J = 7.3 Hz, 2H), 2.77 (dd, J = 12.9, 6.1 Hz, 2H), 2.44 (s, 3H), 2.07 – 1.92 (m, 1H), 1.88 – 1.75 (m, 2H), 1.62 – 1.57 (m, 6H). 13C NMR (63 MHz, D2O) δ 136.5, 132.6, 129.8, 128.9, 46.6, 34.4, 28.5, 20.4, 18.5, 11.2. Anal. Calcd for C12H18S: 194.1129. Found: 193.0889 (M-1). GC RT 6.95 minutes.
(Perfluorophenyl)(p-tolyl)sulfane49: 1H NMR (250 MHz, D2O) δ 7.27 (d, J = 7.3 Hz, 2H), 7.08 (d, J = 7.0 Hz, 2H), 2.29 (s, 3H). 13C NMR (63 MHz, D2O) δ 150.6, 141.7, 140.0, 136.0, 133.7, 131.5, 130.2, 102.2, 24.8. Anal. Calcd for C13H7F5S: 290.0189. Found: 289.0471 (M-1). GC RT 8.60 minutes.

ACKNOWLEDGEMENTS
We wish to thank the Robert H. Cole Foundation for support of this research.

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