Copper mediated formation of carbon-heteroatom bonds using organoboron reagents and ultrasound

Article abstract of DOI:10.3987/COM-14-S(K)18

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.

Full text of DOI:10.3987/COM-14-S(K)18

HETEROCYCLES, Vol. 90, No. 1, 2015
271
HETEROCYCLES, Vol. 90, No. 1, 2015, pp. 271 - 297. © 2015 The Japan Institute of Heterocyclic Chemistry
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*
Department of Chemistry, The University of Tennessee, Knoxville, Tennessee,
USA.
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

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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.
Table 1. Reaction of Arylboronic Acids with Phenols
Starting Material
Starting Boronic Acid
Product
Yield
92

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81
97
91
88
93
92
53
OH
O2N
O
N OH
O
97
88
90
97
OH
NC
O
Br
CF3
91

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81
89
88
O
O
O
OH
CN
NC
O
76
72
OH
66
76
72
OH
NC
68
N
O
CN
85
88

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92
93
O
NC
Reaction conditions: 1.5 mmol of arylboronic acid, 1.0 mmol phenol, 2.0 mmol copper(II)
acetate, 5.0 mmol of triethylamine was mixed in DCM. The mixture was sonicated for 4 hours.
Table 2. Reactions of Arylboronic Acid with Anilines and Indoles
Starting Material
Starting Boronic Acid
Product
Yield
90
87
94
NH2
H
N
NH2
Cl
Cl
89
96
N
97
95
N
N
N
N
H
H
N

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87
91
N
O
86
96
NH2
93
92
97
H
N
CF3
N
CF3
O
92
90
93
NH2
Cl
N
O
O

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78
62
66
H
NH2
N
OH
68
72
61
NH2
NH2
Cl
66
82
81
93
67
NH2

278
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74
90
96
O
N
H
Reaction conditions: 1.5 mmol of arylboronic acid, 1.0 mmol phenol, 2.0 mmol copper(II)
acetate, 5.0 mmol of triethylamine was mixed in DCM. The mixture was sonicated for 4
hours.
Table 3. Reactions of Naphthaboronic Acid with Thiols
Starting Material
Starting Boronic Acid
Product
Yield
92
SH
88
94
93
SH
91
92
SH
Cl

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95
98
95
F
F
F
F
F
F
F
F
F
F
S
SH
95
91
SH
98
92
94
98
SH
Cl
F
F
F
F
F
F
F
F
F
S
CF3
SH
F
90
SH

280
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88
89
87
93
88
S
Cl
O
73
O2N
S
OH
71
73
SH
81
96
HO
S
SH
Cl
Cl

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281
80
76
SH
82
77
98
SH
N
S
92
88
95
85
SH
94
98
S
SH
Cl
Cl

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98
F
F
F
F
F
F
F
F
F
F
S
SH
Reaction conditions: 1.5 mmol of arylboronic acid, 1.0 mmol phenol, 2.0 mmol copper(II)
acetate, 5.0 mmol of triethylamine were mixed in DCM. The mixture was sonicated for 4
hours.
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
and 87% using
2-phenoxynaphthalene,
78% using N-phenylnaphthalen-2-amine,
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:
Table 4. Correlation of Reactant Sigma Values with Product Yields
R ↓ R' →
p-OMe
H
m -OH m-NMe2 p-Me para -C(O)Me p -CF3
0
0
0
0
0
76
76
66
72
72
0
85
93
92
88
91
88
89
81
97
97
90
88
p-Br
p-CN
68
0
2,6–Me

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Table 5. Correlation of Reactant Sigma Values with Product Yields
Y
R ↓
R' →m -OH m -NMe2 p -Me p -C(O)Me p -CF3
NH p-Me
0
0
82
81
90
96
90
93
92
97
NMe p-OMe
NMe H
78
62
66
0
68
72
61
66
93
67
74
0
0
91
86
96
93
NH
H
0
NH p-Cl
92
0
NMe p-NO2
Table 6. Correlation of Reactant Sigma Values with Product Yields
R ↓
R' →
m-OH m-NMe2 p-Me p-C(O)Me p-CF3
p-Me
p-OMe
H
71
0
82
0
95
0
89
0
98
0
0
80
0
92
94
88
85
98
98
90
93
88
87
95
92
91
0
p-Cl
81
73
73
p-NO2
2,6-Me
76
77
0
2,3,4,5,6 -F
94
98
2-methylbutyl
96
98
88
The data indicate that the highest product yields are obtained when the boronic acid contains an electron
withdrawing group, while the phenol has a sigma value close to zero.

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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.
1
2-Phenoxynaphthalene7: H 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.
1
4-(Naphthalen-2-yloxy)benzonitrile9: H 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

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285
minutes.
1
2-(4-Nitrophenoxy)naphthalene10: H 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.
1
2-(3-Methoxyphenoxy)naphthalene10: H 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.
1
2-(4-Iodophenoxy)naphthalene11: H 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.
1
2-(Naphthalen-2-yloxy)isoindoline-1,3-dione12: H 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.
GC RT 12.87 minutes.
Anal. Calcd for C14H8F3NO: 263.0558. Found: 262.0722 (M-1).

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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,

HETEROCYCLES, Vol. 90, No. 1, 2015
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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.

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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.

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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:

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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,

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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),

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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),
13
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). C
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:

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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),

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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,

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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.

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