Tetrahedron Letters

Supporting Information

N-Picolinicamide Derivatives as Ligands in Ullman Type C-O Coupling Reaction

∗
Fehmi Damkaci, Cihad Sigindere, Thomas Sobiech, Erik Vik, and Joshua Malone
Department of Chemistry, SUNY Oswego, Oswego NY 13126, USA

Table of contents

A. General Procedures: Page 2

B. Characterization of products: Page 3-9
C. 1H and 13C Spectra: Page 10-
General:
1
H and 13C NMR spectra were recorded on Bruker 300 or 500 MHz Ultrashield spectrometer. CDCl3 was used as the reference
point in 1H and 13C NMR spectra (7.26 ppm and 77.0 ppm, respectively). Coupling constants (J values) are given in hertz (Hz). Spin
multiplicities are indicated by the following symbols: s (singlet), d (doublet), t (triplet), q (quartet), p (pentet), m (multiplet), and br
(broad).
IR spectra were recorded on a Thermo Scientific Nicolet IR1000 Spectrometer. Band positions are given in reciprocal
centimeters (cm-1). Melting points were taken in soft glass capillary tubes using an uncalibrated Melt-Temp II capillary melting point
apparatus. MS (EI) data were recorded with TRACE-ISQ, GC coupled with quadrapole mass spectrometer.
Microwave irradiation was performed using a CEM Discover SP - Microwave Synthesizer. Analytical thin-layer
chromatography (TLC) was performed on silica gel plates with UV indicator. Flash chromatography was performed with 60 Angstrom
grade silica gel.
Anhydrous tetrahydrofuran (THF) and anhydrous acetonitrile (MeCN) were obtained from an MBraun solvent purification
system. Anhydrous dimethylformamide (DMF), anhydrous dimethlysulfoxide (DMSO), and anhydrous dioxane were purchased from
Acros Organics, bronze powder from Alfa Aesar. Activated copper, NPPA, and NPPA-O were prepared according to the literature
procedures.1 Anhydrous Pyridine and aniline were obtained by distillation under nitrogen from calcium hydride. All other
compounds were used as received. All reactions were conducted in oven-dried (120°C) glassware.

General procedures for the synthesis of diaryl ethers (Tables 1-4)

To a 50mL multi-necked round bottom flask, 1 mmol of aryl halide, 1.2 mmol of phenol, 20 mol% ligand, 20 mol% copper
powder, 2.0 mmol of base, and 20 mL of dry solvent were added. The mixture was stirred at 82 °C for 24h. The reaction mixture was
diluted with ethyl acetate and filtered through Celite in a fritted filter funnel to remove any inorganic salts. The solvent was then
removed with the help of a rotary evaporator. The residue was purified by flash chromatography using hexane and ethyl acetate as
an eluent to result the product.

General procedures for the synthesis of phenols (Tables 5 and 6)

To a 10 mL pressure vessel, aryl halide (1.00 mmol), copper (I) oxide (0.05 mol), ligand (0.05 mol), 3M sodium hydroxide (2
mL), and organic solvent (2 mL) were added. The reaction mixture was irradiated at 160°C for 10 min with strong stirring. The
reaction mixture was allowed to cool to room temperature. The reaction mixture was filtered through a plug of celite in a fritted
filter funnel and washed with ethyl acetate. The product was extracted using three times with 30 mL of ethyl acetate. The organic

1
Damkaci, F.; Altay, E.; Waldron, M.; Knopp, M.; Snow, D.; Massaro, N. Tetrahedron Lett., 2014, 55, 690-693.

2
extract is washed three times with 10 mL water and two times with 10 mL of brine. The organic phase was dried over anhydrous
MgSO4 and the solvent was removed under reduced pressure to provide the product.

1,3-dimethyl-5-phenoxy benzene (Table 2, entry 1)

Synthesized by following experimental procedures for diaryl ether synthesis in 83% yield as yellowish clear oil. 1H
NMR (CDCl3, 300 MHz) δ 2.25 (s, 6H), 6.60 (s, 2H), 6.71 (s, 1H), 6.96 (d, J=9.0, 2H), 7.05 (t, J=9.0, 1H), 7.29 (t, J=9.0,
13
2H). C NMR (CDCl3, 75 MHz) δ 21.3, 116.6, 118.9, 123.0, 125.0, 129.7, 139.6, 157.2, 157.5. IR (diamond) ν (cm-1): 687, 755, 1216,
1489, 1582, 2860, 2916, 3021. MS (EI, m/z): 198 (M+).

1-[4-(3,5-dimethylphenoxy)phenyl] ethanone (Table 2, entry 2)

Synthesized by following experimental procedures for diaryl ether synthesis in 65% yield as white solid; m.p.
80.9 – 81.4°C. 1H NMR (CDCl3, 500 MHz) δ 2.31 (s, 6H) 2.57 (s, 3H) 6.69 (s, 2H) 6.84 (s, 1H) 6.99 (d, J = 9.0, 2H)
7.93 (d, J = 9.0, 2H). 13C NMR (CDCl3, 125 MHz) δ21.3, 26.4, 117.2, 117.8, 126.3, 130.5, 131.7, 140.0, 155.4, 162.2, 196.7. IR
(diamond) ν (cm-1): 586, 834, 1163, 1229, 1265, 1584, 1678, 2918. MS (EI, m/z): 240 (M+).

1-(2-methoxyphenoxy)-3,5-dimethyl benzene (Table 2, entry 3)

Synthesized by following experimental procedures for diaryl ether synthesis in 30% yield as brown oil. 1H NMR
(CDCl3, 300 MHz) δ 2.23 (s, 6H), 3.80 (s, 3H), 6.55 (s, 2H) 6.66 (s, 1H), 6.85 – 6.98 (m, 3H), 7.08 (t, J=9.0, 1H). 13C
NMR (CDCl3, 75 MHz) δ 21.4, 56.0, 112.9, 115.0, 121.1, 124.3, 124.6, 139.3, 145.3, 151.5, 157.9. IR (diamond) ν (cm-1): 685, 748, 834,
1025, 1212, 1254, 1294, 1454, 1497, 1582, 2836, 2919. MS (EI, m/z): 228 (M+).

1-(4-methoxyphenoxy)-3,5-dimethyl benzene (Table 2, entry 4)

Synthesized by following experimental procedures for diaryl ether synthesis in 58% yield as light yellow solid;
m.p. 67 – 68 °C. 1H NMR (CDCl3, 300 MHz) δ 2.22 (s, 6H) 3.76 (s, 3H) 6.53 (s, 2H) 6.65 (s, 1H) 6.84 (d, J = 9.0, 2H)
6.94 (d, J = 9.0, 2H). 13C NMR (CDCl3, 75 MHz) δ 21.4, 55.6, 114.8, 115.3, 120.9, 124.2, 139.5, 150.3, 155.8, 158.5. IR (diamond) ν (cm-
1
): 751, 838, 1032, 1211, 1499, 1588, 2832, 2916, 2948, 2999. MS (EI, m/z): 228 (M+). HRMS (EI) calculated for C14H16O2 [M+]
228.1150, found 228.1196.

1,3-dimethyl-5-(2-methylphenoxy) benzene (Table 2, entry 5)

Synthesized by following experimental procedures for diaryl ether synthesis in 45% yield as clear oil. 1H NMR
(CDCl3, 300 MHz) δ 2.26 (s, 6H) 2.27 (s, 3H) 6.55 (s, 2H) 6.70 (s, 1H) 6.91 (d, J = 9.0 Hz, 1H) 7.06 (t, J = 9.0 Hz, 1H)

3
7.16 (t, J = 9.0 Hz, 1H) 7.25 (d, J = 9.0 Hz, 1H). 13C NMR (CDCl3, 75 MHz) δ 16.3, 21.4, 115.1, 119.8, 123.8, 124.2, 127.2, 130.0, 131.4,
139.6, 154.7, 158.0. IR (diamond) ν (cm-1): 750, 1137, 1185, 1227, 1294, 1488, 1581, 2917, 3020. MS (EI, m/z): 212 (M+).

1,3-dimethyl-5-(4-methylphenoxy) benzene (Table 2, entry 6)

Synthesized by following experimental procedures for diaryl ether synthesis in 87% yield as brown oil. 1H NMR
(CDCl3, 300 MHz) δ 2.30 (s, 6H) 2.36 (s, 3H) 6.65 (s, 2H) 6.74 (s, 1H) 6.95 (d, J = 9.0 Hz, 2H) 7.15 (d, J = 9.0 Hz, 2H).
13
C NMR (CDCl3, 75 MHz) δ 20.8, 21.4, 116.1, 119.2, 124.6, 130.2, 132.7, 139.5, 155.0, 157.8. IR (diamond) ν (cm-1): 686, 816, 1218,
1297, 1504, 1592, 2919, 3028. MS (EI, m/z): 212 (M+).

1,3-dimethyl-5-(2-nitrophenoxy) benzene (Table 2, entry 7)

Synthesized by following experimental procedures for diaryl ether synthesis in 76% yield as orange oil. 1H NMR
(CDCl3, 300 MHz) δ 2.23 (s, 6H), 6.60 (s, 2H), 6.75 (s, 1H), 6.94 (d, J = 9.0 Hz, 1H), 7.10 (t, J = 9.0 Hz, 1H), 7.42 (t, J =
9.0 Hz, 1H), 7.87 (d, J = 9.0 Hz, 1H).13C NMR (CDCl3, 75 MHz) δ 21.3, 117.0, 120.3, 122.8, 125.7, 126.4, 134.1 , 140.0,
151.1, 155.6, 11 Peaks are expected, 10 Peaks are observed. IR (diamond) ν (cm-1): 666.58, 744.24, 858.79, 1235.44, 1522.78,
1586.85, 2858.53, 2918.71, 2971.13, 3015.79. MS (EI, m/z): 243 (M+).

1,3-dimethyl-5-(3-nitrophenoxy) benzene (Table 2, entry 8)

Synthesized by following experimental procedures for diaryl ether synthesis in 78% yield as brown oil. 1H NMR
(CDCl3, 300 MHz) δ 2.25 (s, 6H), 6.61 (s, 2H), 6.78 (s, 1H), 7.24 (d, J = 9.0 Hz, 1H), 7.39 (t, J = 9.0 Hz, 1H), 7.70 (s, 1H),
7.84 (d, J = 9.0 Hz, 1H). 13C NMR (CDCl3, 75 MHz) δ 21.3, 112.7, 117.3, 117.5, 124.1, 126.6, 130.2, 140.2, 149.3,
155.4, 158.8. IR (diamond) ν (cm-1): 676, 737, 808, 1228, 1292, 1346, 1528, 2859, 2920, 2959, 3020. MS (EI, m/z): 243 (M+). HRMS (EI)
calculated for C14H13NO3 [M+] 243.0895, found 243.0872.

1,3-dimethyl-5-(4-nitrophenoxy) benzene (Table 2, entry 9)

Synthesized by following experimental procedures for diaryl ether synthesis in 93% yield as yellow solid, m.p.
59 – 60 °C. 1H NMR (CDCl3, 500 MHz) δ 2.25 (s, 6H) 6.63 (s, 2H) 6.81 (s, 1H) 6.91 (d, J = 9.0 Hz, 2H) 8.09 (d, J =
9.0 Hz, 2H). 13C NMR (CDCl3, 75 MHz) δ 21.3, 117.0, 118.1, 125.9, 127.1, 140.3, 142.4, 154.6, 163.6. IR
(diamond) ν (cm-1): 684, 757, 846, 1134, 1233, 1291, 1342, 1487, 1499, 1581, 2856, 2924, 2957. MS (EI, m/z): 243 (M+). HRMS (EI)
calculated for C14H13NO3 [M+] 243.0895, found 243.0904.

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 1-[(2-iodophenyl)methoxy]-3,5-dimethyl benzene (Figure 2)
Synthesized by following experimental procedures for diaryl ether synthesis in 85% yield as yellow oil. 1H NMR
(CDCl3, 300 MHz) δ 2.27 (s, 6H), 4.96 (s, 2H), 6.59 (s, 3H), 6.97 (t, J=9.0, 1H), 7.32 (t, J=9.0, 1H), 7.47 (d, J=9.0, 1H),
7.81 (d, J=9.0, 1H). 13C NMR (CDCl3, 75 MHz) δ 21.7, 73.9, 97.5, 112.9, 123.2, 128.8, 128.9, 129.2, 139.3, 139.4,
139.5, 158.7. MS (EI, m/z): 338 (M+). HRMS (EI) calculated for C15H15IO [M+] 338.0168, found 338.0186.

1-[(2-chlorophenyl)methoxy]-3,5-dimethyl benzene (Figure 2)

Synthesized by following experimental procedures for diaryl ether synthesis in 74% yield as orange oil. 1H NMR
(CDCl3, 500 MHz) δ 2.32 (s, 6H) 5.14 (s, 2H) 6.66 (s, 3H) 7.22 – 7.31 (m, 2H) 7.40 (d, J = 9.0, 1H) 7.58 (d, J = 9.0,
1H). 13C NMR (CDCl3, 75 MHz) δ 21.5, 66.9, 112.6, 123.0, 127.0, 128.8, 128.9, 129.3, 132.5, 135.1, 139.3, 158.6. IR
(diamond) ν (cm-1): 748, 1153, 1295, 1590, 2852, 2920, 3019, 3072. MS (EI, m/z): 246 (M+). HRMS (EI) calculated
+
for C15H15ClO [M ] 246.0811, found 246.0844.

1-methoxy-4-phenoxy benzene (Table 3, entry 1)

Synthesized by following experimental procedures for diaryl ether synthesis in 71% yield as tan oil. 1H NMR
(CDCL3, 300 MHz) δ 3.75 (s, 3H), 6.82 – 7.01 (m, 7H), 7.24 (t, J = 9.0, 2H). 13C NMR (CDCl3, 75 MHz) δ 55.6, 114.9,
117.6, 120.8, 122.4, 129.6, 150.1, 155.9, 158.5. IR (diamond) ν (cm-1): 690, 755, 838, 1033, 1213, 1486, 1502, 1588,
2834, 2906, 2951, 3000. MS (EI, m/z): 200 (M+).

1-methyl-4-phenoxy benzene (Table 3, entry 2)

Synthesized by following experimental procedures for diaryl ether synthesis in 76% yield as yellow oil. 1H NMR
(CDCl3, 500 MHz) δ 2.35 (s, 3H), 6.94 (d, J = 8.5 Hz, 2H), 7.00 (d, J=8.5, 2H), 7.08 (t, J = 8.5 Hz, 1H), 7.15 (d, J = 8.5
Hz, 2H), 7.33 (t, J = 8.5 Hz, 2H). 13C NMR (CDCl3, 75 MHz) δ 20.7, 118.4, 119.1, 122.8, 129.7, 130.3, 132.9, 154.7, 157.8. IR (diamond) ν
(cm-1): 689, 755, 870, 1165, 1231, 1487, 1507, 1588, 2858, 2918, 3025, 3062. MS (EI, m/z): 184 (M+).

1-nitro-4-phenoxy benzene (Table 3, entry 3)

Synthesized by following experimental procedures for diaryl ether synthesis in 84% yield as yellowish solid;, m.p.
56 – 58 °C. 1H NMR (CDCl3, 500 MHz) δ 7.01 (d, J = 10.0, 2H) 7.09 (d, J = 10.0, 2H) 7.26 (t, J = 10.0, 1H) 7.44 (t, J =
10.0, 2H) 8.19 (d, J = 10.0, 2H). 13C NMR (CDCl3, 75 MHz) δ 117.1, 120.6, 125.4, 125.9, 130.3, 142.6, 154.7, 163.4. IR (diamond) ν (cm-
1
): 688, 749, 1110, 1239, 1340, 1483, 1511, 1581, 2850, 2920. MS (EI, m/z): 215 (M+). HRMS (EI) calculated for C12H9NO3 [M+]
215.0582, found 215.0591.

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 1-methyl-2-(4-methylphenoxy) benzene (Table 3, entry 6)
Synthesized by following experimental procedures for diaryl ether synthesis in 79% yield as clear oil. 1H NMR
(CDCl3, 300 MHz) δ 2.28 (s, 3H) 2.33 (s, 3H) 6.82 – 6.91 (m, 3H), 7.02 – 7.19 (m, 4H), 7.25 (d, J = 9.0 Hz, 1H). 13C
NMR (CDCl3, 75 MHz) δ 16.3, 20.7, 117.6, 119.3, 123.7, 127.1, 129.8, 130.2, 131.4, 131.9, 155.1, 155.7. IR (diamond) 729, 812, 875,
1111, 1233, 1487, 1505, 1585, 2862, 2923, 3028. MS (EI, m/z): 198 (M+).

1-methyl-2-(4-nitrophenoxy) benzene (Table 3, entry 7)

Synthesized by following experimental procedures for diaryl ether synthesis in 88% yield as yellow oil. 1H NMR
(CDCl3, 300 MHz) δ 2.10 (s, 3H), 6.84 (d, J = 9.0, 2H), 6.94 (d, J = 9.0, 1H), 7.09 – 7.25 (m, 3H), 8.10 (d, J = 9.0,
13
2H). C NMR (CDCl3, 75 MHz) δ 16.0, 116.0, 121.2, 126.0, 126.0, 127.8, 130.5, 132.0, 142.3, 152.4, 163.4. IR (diamond) ν (cm-1): 743,
847, 1108, 1241, 1338, 1484, 1510, 1579, 2926. MS (EI, m/z): 229 (M+). HRMS (EI) calculated for C13H11NO3 [M+] 229.0739, found
229.0712.

1-methoxy-4-(4-methylphenoxy) benzene (Table 3, entry 10)

Synthesized by following experimental procedures for diaryl ether synthesis in 83% yield as brown oil. 1H NMR
(CDCl3, 500 MHz) δ 2.35 (s, 3H), 3.82 (s, 3H), 6.90 (m, 4H), 7.00 (d, J = 9.0, 2H), 7.14 (d, J=9.0, 2H). 13C NMR
(CDCl3, 75 MHz) δ 20.6, 55.6, 114.8, 117.8, 120.3, 130.1, 132.0, 15.7, 155.6, 156.1. IR (diamond) 813, 1031, 1101, 1227, 1257, 1498,
1608, 2836, 2855, 2913, 2957. MS (EI, m/z): 214 (M+). HRMS (EI) calculated for C14H14O2 [M+] 214.0994, found 214.0981.

1-methoxy-4-(4-nitrophenoxy) benzene (Table 3, entry 11)

Synthesized by following experimental procedures for diaryl ether synthesis in 92% yield as tannish solid; m.p.
111 – 112 °C. 1H NMR (CDCl3, 500 MHz) δ 3.83 (s, 3H) 6.93 – 6.95 (m, 2H) 7.02 (d, J = 9.0, 2H) 8.16 (d, J = 9.5,
2H). 13C NMR (CDCl3, 75 MHz) δ 55.7, 115.3, 116.4, 121.9, 125.9, 142.3, 147.8, 157.2, 164.2. IR (diamond) ν
(cm-1): 746, 843, 1031, 1237, 1328, 1338, 1485, 1501, 1584, 1608 2846, 2922, 2953. MS (EI, m/z): 245 (M+).

1,3-dimethyl-5-phenoxy-2-pyridine (Table 4, entry 1)

Synthesized by following experimental procedures for diaryl ether synthesis in 53% yield as orange oil. 1H NMR
(CDCl3, 300 MHz) δ 2.26 (s, 6H) 6.70 (s, 2H) 6.78 (s, 1H) 6.81 (d, J = 9.0, 1H) 6.90 (t, J = 6.0, 1H) 7.59 (t, J = 6.0, 1H)
8.15 (d, J = 3.0, 1H). 13C NMR (CDCl3, 75 MHz) δ 21.4, 111.5, 118.3, 118.8, 126.6, 139.3, 139.5, 147.9, 154.1, 164.0.

6
IR (diamond) ν (cm-1): 775, 1136, 1242, 1294, 1427, 1464, 1570, 1582, 2914. MS (EI, m/z): 198 (M+).

2-chloro-6-(3,5-dimethylphenoxy) pyridine (Table 4, entry 3)

Synthesized by following experimental procedures for diaryl ether synthesis in 57% yield as yellowish oil. 1H
NMR (CDCl3, 300 MHz) δ 2.24 (s, 6H) 6.61 (d, J = 9.0 Hz, 1H) 6.67 (s, 2H) 6.77 (s, 1H) 6.93 (d, J = 9.0 Hz, 1H) 7.50
(t, J = 9.0 Hz, 1H). 13C NMR (CDCl3, 75 MHz) δ 21.3, 108.9, 118.3, 118.5, 126.9, 139.7, 141.4, 149.1, 153.7, 163.5.
IR (diamond) ν (cm-1): 797, 1136, 1161, 1259, 1277, 1294, 1426, 1573, 2852, 2920, 2953. MS (EI, m/z): 233 (M+).

3-(4-nitrophenoxy) pyridine (Table 4, entry 4)

Synthesized by following experimental procedures for diaryl ether synthesis in 95% yield as orange solid; m.p.
106 – 108.0 °C. 1H NMR (CDCl3, 500 MHz) δ 6.97 (d, J = 9 Hz, 2H) 7.36 – 7.43 (m, 2H), 8.21 (d, J=9, 2H) 8.50 (d,
J=17.5, 2H). 13C NMR (CDCl3, 75 MHz) δ 117.4, 136.1, 127.7, 142.6, 143.3, 146.3, 162.3 (9 Peaks are expected, 7 Peaks were
observed). IR (diamond) ν (cm-1): 705, 748, 849, 1109, 1241, 1252, 1337, 1501, 1571, 1592, 2853, 2923. MS (EI, m/z): 216 (M+).

1-methyl-4-[(4-nitrophenyl)thio] benzene (Table 4, entry 6)

Synthesized by following experimental procedures for diaryl ether synthesis in 93% yield as yellowish solid;
m.p. 77.3 – 78.4 °C. 1H NMR (CDCl3, 500 MHz) δ 2.42 (s, 3H), 7.13 (d, J = 9.0, 2H), 7.27 (d, J = 9.0, 2H), 7.44 (d, J
= 9.0, 2H), 8.04 (d, J = 9.0, 2H). 13C NMR (CDCl3, 125 MHz) δ 21.3, 123.9, 126.1, 126.5, 130.8, 135.0, 140.2, 145.1, 149.3. IR (diamond)
ν (cm-1): 738, 812, 841, 1336, 1509, 1573, 1592, 2852, 2922. MS (EI, m/z): 245 (M+).

OHPhenol (Table 6, entry 1)

Synthesized by following general procedure providing the product as a colorless solid in 96% yield; m.p. 41 – 42°C (lit.[2]
40.91°C ); IR (diamond) ν (cm-1): 3227 (br), 1570 (s), 1490 (s), 1471 (s), 1369 (s), 1221 (s) 808 (s), 746 (s); 1H NMR (300 MHz,
CDCl3) δ 7.26 (d, J = 9.0 Hz, 2H), 6.95 (t, J = 9.0 Hz, 1H), 6.85 (d, J = 9.00 Hz, 2H), 4.42 (s, 1H); 13C NMR (75 MHz, CDCl3) δ 115.4, 129.7,
120.9, 115.3.

OH 4-nitrophenol (Table 6, entry 2)

Synthesized by following general procedure providing the product as a yellow solid in 98% yield; m.p. 113 – 114°C
O2N (lit.[3] 113 – 114°C ); IR (diamond) ν (cm-1): 3358 (br), 3084 (w), 1592 (s), 1488 (s), 1333 (s), 1299 (s), 1107 (s), 849 (s);

2
Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Volumes 1: New York, NY. John Wiley and Sons, 1991-Present., p. V18 (1996) 592.

7
1
H NMR (300 MHz, CDCl3) δ 8.12 (d, J = 9.0 Hz, 2H), 6.86 (d, J = 9.0 Hz, 2H), 5.58 (s, 1 H); 13C NMR (75 MHz, CDCl3) δ 161.4, 141.6, 126.3,
115.8. MS (EI, m/z): 139 (M+).

O2N OH 3-nitrophenol (Table 6, entry 3)

Synthesized by following general procedure providing the product as a yellow solid in 44% yield; m.p. 96 – 97°C (lit.[4]
96.8°C ); IR (diamond) ν (cm-1): 3382 (br), 1620 (w), 1519 (s), 1347 (s), 1294 (s), 1209 (s), 800 (s), 744 (s); 1H NMR (300
MHz, CDCl3) δ 7.82 (d, J = 9.0 Hz, 1H), 7.70 (s, 1H), 7.41 (t, J = 9.0 Hz, 1H), 7.19 (d, J = 9.0 Hz, 1H), 5.51 (s, 1H); 13C NMR (75 MHz, CDCl3) δ
156.2, 149.1, 130.3, 122.0, 116.0, 110.6. MS (EI, m/z): 139 (M+).

4-methoxyphenol (Table 6, entry 4)

OH
Synthesized by following general procedure providing the product as a waxy white solid in 98% yield; m.p. 54 – 55°C
MeO (lit.[5] 54°C ); IR (diamond) ν (cm-1): 3385 (br), 3033 (w), 2952 (w), 2834 (w), 1507 (s), 1217 (s) 1075 (s) 824 (s); 1H NMR
(300 MHz, DMSO) δ 8.88 (s, 1H), 6.73 (d, J = 12.0 Hz, 2H), 6.67 (d, J = 12.0, 2H), 3.65 (s, 3H); 13C NMR (75 MHz, CDCl3) δ
153.7, 149.5, 116.1, 114.9, 55.8.

OH 2-methoxyphenol (Table 6, entry 5)

Synthesized by following general procedure providing the product as a yellowish oil in 53% yield; IR (diamond) ν (cm-1):
1
OMe 3385 (br), 1507 (s), 1444 (w), 1218 (s); H NMR (300 MHz, CDCl3) δ 7.14 (t, J = 6.0 Hz, 1H), 6.95-6.84 (m, 4H), 5.65 (s, 1H),
3.87 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 145.7, 121.5, 120.1, 114.5, 110.7, 55.8.

OH 4-bromophenol (Table 6, entry 6)

Synthesized by following general procedure providing the product as a reddish solid in 72% yield; m.p. 66 – 67°C (lit.[6]
Br 66.4°C ); IR (diamond) ν (cm-1): 3316 (br), 1587 (w), 1496 (s), 1433 (w), 1215 (s), 1067 (s), 816 (s); 1H NMR (300 MHz,
CDCl3) δ 7.32 (d, J = 9.0 Hz, 2H), 6.71 (d, J = 9.0 Hz, 2H), 4.89 (s, 1H); 13C NMR (75 MHz, CDCl3) δ 154.6, 132.5, 117.2, 112.9.

3
O'Neil, M.J. (ed.). The Merck Index - An Encyclopedia of Chemicals, Drugs, and Biologicals. Whitehouse Station, NJ: Merck and Co., Inc., 2006., p. 1145.
4
Haynes, W.M. (ed.) CRC Handbook of Chemistry and Physics. 91st ed. Boca Raton, FL: CRC Press Inc., 2010-2011, p. 3-392.
5
Haynes, W.M. (ed.). CRC Handbook of Chemistry and Physics. 95th Edition. CRC Press LLC, Boca Raton: FL 2014-2015, p. 3-350.
6
Lide, D.R. CRC Handbook of Chemistry and Physics 86TH Edition 2005-2006. CRC Press, Taylor & Francis, Boca Raton, FL 2005, p. 3-68.

8
 OH 4-chlorophenol (Table 6, entry 7)
Synthesized by following general procedure providing the product as a yellow solid in 51% yield; m.p. 42 – 43°C (lit.[7]
Cl 42.8°C ); IR (diamond) ν (cm-1): 3337 (br), 2922 (s), 2850 (s), 1460 (w), 1258 (s), 1010 (s), 803 (s); 1H NMR (300 MHz,
CDCl3) δ 7.19 (d, J = 9.0 Hz, 2H), 6.76 (d, J = 9.0 Hz, 2H), 5.12 (s, 1H); 13C NMR (75 MHz, CDCl3) δ 154.2, 129.5, 125.6, 116.7.

OH 4-methylphenol (Table 6, entry 8)

Synthesized by following general procedure providing the product as a yellow solid in 55% yield; m.p. 34 – 35°C (lit.[8]
Me 34.8°C ); IR (diamond) ν (cm-1): 3303 (br), 2918 (w), 2850 (s), 1521 (s), 1231 (s), 1002 (s), 816 (s); 1H NMR (300 MHz,
CDCl3) δ 7.03 (d, J = 9.0 Hz, 2H), 6.74 (d, J = 9.0 Hz, 2H), 3.99 (s, 1H), 2.27 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 153.4, 130.1, 129.8, 115.1,
20.5. MS (EI, m/z): 124 (M+).

OH 1-naphthol (Table 6, entry 12)

Synthesized by following general procedure providing the product as a reddish solid in 97% yield; m.p. 93 – 95°C (lit.[9] 93 –
95°C ); IR (diamond) ν (cm-1): 3290 (br), 3045 (w), 1632 (s), 1597 (s), 1515 (s), 1457 (s), 1387 (s), 1364 (s), 1301 (s), 1270 (s),
788 (s), 764 (s); 1H NMR (300 MHz, CDCl3) δ 8.19 (d, J = 9.0 Hz, 1H), 7.83 (d, J = 9.0 Hz, 1H), 7.52-7.44(m, 3H), 7.34-7.26 (m,
1H), 6.83 (d, J = 9.00 Hz, 1 H) ; 13C NMR (75 MHz, CDCl3) δ 151.4, 134.8, 127.7, 126.5, 125.9, 125.3, 124.3, 121.6, 120.7, 108.6. MS (EI,
m/z): 144 (M+).

7
Lide, D.R. CRC Handbook of Chemistry and Physics 86TH Edition 2005-2006. CRC Press, Taylor & Francis, Boca Raton, FL 2005, p. 3-110.
8
Haynes, W.M. (ed.). CRC Handbook of Chemistry and Physics. 95th Edition. CRC Press LLC, Boca Raton: FL 2014-2015, p. 3-128.
9
Sibi, M. P.; Dankwardt, J. W.; Snieckus, V. The Journal of Organic Chemistry 1986, 51 (2), 271–273.

9
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