The Journal of Organic Chemistry
Note
6), 129.6 (CH, C-14), 129.0 (CH, C-10), 128.7 (CH, C-15), 127.8
(CH, C-9), 126.1 (CH, C-16), 124.2 (CH, C-5), 54.9 (CH, C-7),
34.5 (Cq, C-3), 30.3 (CH3, C-4), 20.6 (CH3, C-12). HRMS (ESI)
calcd m/z for [C28H33OS+] [M − H−] 417.2247, found 417.2251.
4-(((4-Bromophenyl)thio)(p-tolyl)methyl)-2,6-di-tert-butylphenol
(4d). According to the General Procedure, the thiophenol 1d-H (7.7
mg, 0.041 mmol) and the pQM 2d (12.0 mg, 0.0389 mmol) were
mixed. The reaction mixture (in 1.2 mL DMSO-d6) was analyzed by
4-(((3,5-Bis(trifluoromethyl)phenyl)thio)(p-tolyl)methyl)-2,6-di-
tert-butylphenol (4h). According to the General Procedure, the
thiophenol 1h-H (10.0 mg, 0.0408 mmol) and the pQM 2d (12.0 mg,
0.0389 mmol) were mixed. The reaction mixture (in 1.2 mL DMSO-
1
d6) was analyzed by NMR spectroscopy and HRMS. H NMR (400
MHz, DMSO-d6) δ 7.86 (s, 2 H, 14-H), 7.76 (br s, 1 H, 16-H), 7.43−
7.41 (m, 2 H, 9-H), 7.22 (s, 2 H, 5-H), 7.14 (d, J = 7.9 Hz, 2 H, 10-
H), 6.91 (s, 1 H, 1-OH), 6.14 (s, 1 H, 7-H), 2.24 (s, 18 H, 4-H), 1.30
(s, 3 H, 12-H). 13C{1H} NMR (101 MHz, DMSO-d6) δ 153.0 (Cq,
C-1), 140.4 (Cq, C-13), 139.2 (Cq, C-2), 137.4 (Cq, C-8), 136.6 (Cq,
C-11), 130.5 (Cq, C-6), 130.3 (q, JC,F = 32.9 Hz, Cq, C-15), 129.5 (br,
CH, C-14), 129.2 (CH, C-10), 127.8 (CH, C-9), 124.5 (CH, C-5),
123.0 (q, JC,F = 273 Hz, Cq, C-17), 119.1 (br, CH, C-16), 54.2 (CH,
C-7), 34.5 (Cq, C-3), 30.1 (CH3, C-4), 20.6 (CH3, C-12). HRMS
(ESI) calcd m/z for [C30H31F6OS+] [M − H−] 553.1994, found
553.2000.
1
NMR spectroscopy and HRMS. H NMR (600 MHz, DMSO-d6) δ
7.37 (d, J = 8.6 Hz, 4 H, 9-H and 14/15-H), 7.21 (d, J = 8.6 Hz, 2 H,
14/15-H), 7.14 (s, 2 H, 5-H), 7.10 (d, J = 7.9 Hz, 2 H, 10-H), 6.92 (s,
1 H, 1-OH), 5.79 (s, 1 H, 7-H), 2.23 (s, 3 H, 12-H), 1.31 (s, 18 H, 4-
H). 13C{1H} NMR (151 MHz, DMSO-d6) δ 152.9 (Cq, C-1), 139.1
(Cq, C-2), 138.3 (Cq, C-8), 136.2 (Cq, C-11), 135.6 (Cq, C-13), 131.6
(CH, C-14 or C-15), 131.54 (Cq, C-6), 131.48 (CH, C-14 or C-15),
129.0 (CH, C-10), 127.8 (CH, C-9), 124.3 (CH, C-5), 119.2 (Cq, C-
16), 54.9 (CH, C-7), 34.5 (Cq, C-3), 30.3 (CH3, C-4), 20.6 (CH3, C-
12). HRMS (ESI) calcd m/z for [C28H3279BrOS+] [M − H−]
495.1352, found 495.1357; calcd m/z for [C28H3281BrOS+] [M − H−]
497.1331, found 497.1337.
2,6-Di-tert-butyl-4-(((4-nitrophenyl)thio)(p-tolyl)methyl)phenol
(4i). According to the General Procedure, the thiophenol 1i-H (6.3
mg, 0.041 mmol) and the pQM 2d (12.0 mg, 0.0389 mmol) were
mixed. The reaction mixture (in 1.2 mL DMSO-d6) was analyzed by
1
NMR spectroscopy and HRMS. H NMR (400 MHz, DMSO-d6) δ
2,6-Di-tert-butyl-4-(((3-chlorophenyl)thio)(p-tolyl)methyl)phenol
(4e). According to the General Procedure, the thiophenol 1e-H (5.9
mg, 0.041 mmol) and the pQM 2d (12.0 mg, 0.0389 mmol) were
mixed. The reaction mixture (in 1.2 mL DMSO-d6) was analyzed by
8.03 (d, J = 9.0 Hz, 2 H, 15-H), 7.47−7.42 (m, 4 H, 9-H and 14-H),
7.20 (s, 2 H, 5-H), 7.13 (d, J = 7.9 Hz, 2 H, 10-H), 6.97 (s, 1 H, 1-
OH), 6.09 (s, 1 H, 7-H), 2.24 (s, 3 H, 12-H), 1.32 (s, 18 H, 4-H).
13C{1H} NMR (101 MHz, DMSO-d6) δ 153.1 (Cq, C-1), 147.0 (Cq,
1
NMR spectroscopy and HRMS. H NMR (600 MHz, DMSO-d6) δ
7.40 (d, J = 8.1 Hz, 2 H, 9-H), 7.30 (s, 1 H, 18-H), 7.24−7.19 (m, 2
H, 14-H and 15-H), 7.18 (s, 2 H, 5-H), 7.16−7.14 (m, 1 H, 16-H),
7.12 (d, J = 8.0 Hz, 2 H, 10-H), 6.92 (s, 1 H, 1-OH), 5.88 (s, 1 H, 7-
H), 2.24 (s, 3 H, 12-H), 1.32 (s, 18 H, 4-H). 13C{1H} NMR (151
MHz, DMSO-d6) δ 152.9 (Cq, C-1), 139.1 (Cq, C-2), 138.6 (Cq, C-
13), 138.3 (Cq, C-8), 136.2 (Cq, C-11), 133.2 (Cq, C-17), 131.5 (Cq,
C-6), 130.2 (CH, C-15), 129.1 (CH, C-10), 128.5 (CH, C-18),
127.82 (CH, C-14), 127.78 (CH, C-9), 125.9 (CH, C-16), 124.4
(CH, C-5), 54.4 (CH, C-7), 34.6 (Cq, C-3), 30.3 (CH3, C-4), 20.6
(CH3, C-12). HRMS (ESI) calcd m/z for [C28H3235ClOS+] [M −
H−] 451.1857, found 451.1861; calcd m/z for [C28H3237ClOS+] [M −
H−] 453.1827, found 453.1831.
C-13), 144.6 (Cq, C-16), 139.3 (Cq, C-2), 137.7 (Cq, C-8), 136.4 (Cq,
C-11), 130.9 (Cq, C-6), 129.2 (CH, C-10), 127.7 (CH, C-9), 127.4
(CH, C-14), 124.3 (CH, C-5), 123.6 (CH, C-15), 53.3 (CH, C-7),
34.5 (Cq, C-3), 30.2 (CH3, C-4), 20.6 (CH3, C-12) (additional
resonances are caused by a slight excess of the pQM 2d). HRMS
(ESI) calcd m/z for [C28H32NO3S+] [M − H−] 462.2097, found
462.2101.
2,6-Di-tert-butyl-4-((naphthalen-2-ylthio)(p-tolyl)methyl)phenol
(4j). According to the General Procedure, the thiophenol 1j-H (6.5
mg, 0.041 mmol) and the pQM 2d (12.0 mg, 0.0389 mmol) were
mixed. The reaction mixture (in 1.2 mL DMSO-d6) was analyzed by
1
NMR spectroscopy and HRMS. H NMR (600 MHz, DMSO-d6) δ
2,6-Di-tert-butyl-4-(p-tolyl((3-(trifluoromethyl)phenyl)thio)-
methyl)phenol (4f). According to the General Procedure, the
thiophenol 1f-H (7.3 mg, 0.041 mmol) and the pQM 2d (12.0 mg,
0.0389 mmol) were mixed. The reaction mixture (in 1.2 mL DMSO-
7.80 (d, J = 8.0 Hz, 1 H, 17-H), 7.79−7.78 (m, 1 H, 22-H), 7.74 (d, J
= 8.7 Hz, 1 H, 15-H), 7.69 (d, J = 8.2, 1 H, 20-H), 7.47−7.40 (m, 5
H, 9-H, 14-H, 18-H, 19-H), 7.22 (s, 2 H, 5-H), 7.09 (d, J = 8.0 Hz, 2
H, 10-H), 6.90 (s, 1 H, 1-OH), 5.93 (s, 1 H, 7-H), 2.21 (s, 3 H, 12-
H), 1.31 (s, 18 H, 4-H). 13C{1H} NMR (151 MHz, DMSO-d6) δ
152.8 (Cq, C-1), 139.1 (Cq, C-2), 138.7 (Cq, C-8), 136.1 (Cq, C-11),
133.6 (Cq, C-13), 133.1 (Cq, C-21), 131.9 (Cq, C-6), 131.3 (Cq, C-
16), 129.0 (CH, C-10), 128.0 (CH, C-15), 127.9 (CH, C-9), 127.8
(Cq, C-22), 127.7 (CH, C-18), 127.5 (CH, C-17), 126.9 (CH, C-20),
126.5 (CH, C-19), 125.8 (CH, C-14), 124.3 (CH, C-5), 54.8 (CH,
C-7), 34.5 (Cq, C-3), 30.3 (CH3, C-4), 20.6 (CH3, C-12). HRMS
(ESI) calcd m/z for [C32H35OS+] [M − H−] 467.2403, found
467.2409.
1
d6) was analyzed by NMR spectroscopy and HRMS. H NMR (600
MHz, DMSO-d6) δ 7.56 (d, J = 7.5 Hz, 1 H, 14-H), 7.51 (s, 1 H, 18-
H), 7.44−7.41 (m, 2 H, 15-H, 16-H), 7.40 (d, J = 8.2 Hz, 2 H, 9-H),
7.20 (s, 2 H, 5-H), 7.12 (d, J = 7.9 Hz, 2 H, 10-H), 6.91 (s, 1 H, 1-
OH), 5.94 (s, 1 H, 7-H), 2.23 (s, 3 H, 12-H), 1.31 (s, 18 H, 4-H).
13C{1H} NMR (151 MHz, DMSO-d6) δ 152.9 (Cq, C-1), 139.1 (Cq,
C-2), 138.1 (Cq, C-8), 137.9 (Cq, C-13), 136.3 (Cq, C-11), 133.3 (br,
CH, C-14), 131.2 (Cq, C-6), 129.5 (CH, C-15), 129.4 (q, JC,F = 38
Hz, Cq, C-17), 129.1 (CH, C-10), 127.8 (CH, C-9), 125.6 (q, JC,F
=
3.9 Hz, CH, C-18), 124.4 (CH, C-5), 123.8 (q, JC,F = 273 Hz, CF3, C-
19), 122.6 (q, JC,F = 3.7 Hz, CH, C-16), 54.5 (CH, C-7), 34.5 (Cq, C-
3), 30.2 (CH3, C-4), 20.6 (CH3, C-12). HRMS (ESI) calcd m/z for
[C29H32F3OS+] [M − H−] 485.2120, found 485.2125.
2,6-Di-tert-butyl-4-((julolidin-9-yl)(p-tolylthio)methyl)phenol
(4k). According to the General Procedure, the thiophenol 1b-H (6.3
mg, 0.041 mmol) and the pQM 2a (15.2 mg, 0.0389 mmol) were
mixed. The reaction mixture (in 1.2 mL DMSO-d6) was analyzed by
1
NMR spectroscopy and HRMS. H NMR (400 MHz, DMSO-d6) δ
2,6-Di-tert-butyl-4-(p-tolyl((4-(trifluoromethyl)phenyl)thio)-
methyl)phenol (4g). According to the General Procedure, the
thiophenol 1g-H (7.3 mg, 0.041 mmol) and the pQM 2d (12.0 mg,
0.0389 mmol) were mixed. The reaction mixture (in 1.2 mL DMSO-
7.14−7.11 (m, 4 H, 5-H and 16-H), 7.00 (d, J = 8.0 Hz, 2 H, 17-H),
6.82 (s, 1 H, 1-OH), 6.79 (s, 2 H, 9-H), 5.38 (s, 1 H, 7-H), 3.05−3.03
(m, 4 H, 14-H), 2.61 (t, J = 6.4 Hz, 4 H, 12-H), 2.20 (s, 3 H, 19-H),
1.82 (pent, J = 6.4 Hz, 4 H, 13-H), 1.31 (s, 18 H, 4-H). 13C{1H}
NMR (101 MHz, DMSO-d6) δ 152.4 (Cq, C-1), 141.6 (Cq, C-11),
138.8 (Cq, C-2), 135.6 (Cq, C-18), 132.8 (Cq, C-15), 132.7 (Cq, C-6),
130.5 (CH, C-16), 129.3 (CH, C-17), 128.2 (Cq, C-8), 126.2 (CH,
C-9), 124.2 (CH, C-5), 120.6 (Cq, C-10), 56.0 (CH, C-7), 49.2
(CH2, C-14), 34.5 (Cq, C-3), 30.3 (CH3, C-4), 27.2 (CH2, C-12),
21.6 (CH2, C-13), 20.5 (CH3, C-19). HRMS (ESI) calcd m/z for
[C34H44NOS+] [M + H+] 514.3138, found 514.3139.
1
d6) was analyzed by NMR spectroscopy and HRMS. H NMR (600
MHz, DMSO-d6) δ 7.53 (d, J = 8.3 Hz, 2 H, 15-H), 7.44−7.41 (m, 4
H, 9-H and 14-H), 7.17 (s, 2 H, 5-H), 7.12 (d, J = 7.9 Hz, 2 H, 10-
H), 6.95 (s, 1 H, 1-OH), 5.97 (s, 1 H, 7-H), 2.23 (s, 3 H, 12-H), 1.31
(s, 18 H, 4-H). 13C{1H} NMR (151 MHz, DMSO-d6) δ 153.0 (Cq,
C-1), 142.4 (Cq, C-13), 139.2 (Cq, C-2), 138.1 (Cq, C-8), 136.3 (Cq,
C-11), 131.3 (Cq, C-6), 129.1 (CH, C-10), 128.4 (CH, C-14), 127.7
(CH, C-9), 125.8 (q, JC,F = 32.0 Hz, Cq, C-16), 125.4 (q, JC,F = 3.7
Hz, CH, C-15), 124.3 (CH, C-5), 124.2 (q, JC,F = 272 Hz, Cq, C-17),
53.7 (CH, C-7), 34.6 (Cq, C-3), 30.3 (CH3, C-4), 20.6 (CH3, C-12).
HRMS (ESI) calcd m/z for [C29H32F3OS+] [M − H−] 485.2120,
found 485.2124.
2,6-Di-tert-butyl-4-((4-(dimethylamino)phenyl)(p-tolylthio)-
methyl)phenol (4l). According to the General Procedure, the
thiophenol 1b-H (6.3 mg, 0.041 mmol) and the pQM 2b (13.1 mg,
0.0389 mmol) were mixed. The reaction mixture (in 1.2 mL DMSO-
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J. Org. Chem. 2021, 86, 5965−5972