The Journal of Organic Chemistry
Note
was petroleum ether. 1H NMR (500 MHz, CDCl3): δ 7.31 (d, J = 7.8
Hz, 2H), 7.09 (d, J = 7.8 Hz, 2H), 3.03−2.99 (m, 1H), 2.32 (s, 3H),
1.97−1.94 (m, 2H), 1.75−1.59 (m, 2H), 1.59 (m, 1H), 1.37−1.21
(m, 5H). 13C{1H} NMR (125 MHz, CDCl3): δ 136.9, 132.8, 131.2,
129.5, 47.1, 33.4, 26.1, 25.8, 21.1.
13C{1H} NMR (125 MHz, DMSO-d6): δ 206.9, 135.6, 130.8, 130.1,
129.5, 42.5, 30.2, 26.7.
But-3-en-1-yl (4-Chlorophenyl) Sulfide (15).24 Compound 15 was
obtained by NHPI ester 1f (73.6 mg, 0.3 mmol) and 4-
chlorothiophenol (28.9 mg, 0.2 mmol) in the presence of DIPEA
(15.5 mg, 0.12 mmol) in DMA (2 mL) under irradiation to afford
41% (16.3 mg) yield as a colorless liquid. The eluent was petroleum
ether. 1H NMR (500 MHz, CDCl3): δ 7.27−7.24 (m, 4H), 5.86−5.79
(ddt, J = 17.0, 10.3, 6.7 Hz, 1H), 5.05−5.10 (m, 2H), 2.59 (t, J = 7.5
Hz, 2H), 2.59 (q, J = 7.5 Hz, 2H). 13C{1H} NMR (125 MHz,
CDCl3): δ 136.1, 135.0, 131.9, 130.6, 129.0, 116.4, 33.3, 33.2.
(4-Bromophenethyl)(4-chlorophenyl) Sulfide (16). Compound 16
was obtained by NHPI ester 1g (112.3 mg, 0.3 mmol) and 4-
chlorothiophenol (28.9 mg, 0.2 mmol) with DIPEA (15.5 mg, 0.12
mmol) in DMSO (2 mL) in 82% (53.7 mg) yield as a yellow oil. The
Cyclohexyl (4-Methoxyphenyl) Sulfide (8).19 NHPI ester 1d (82.0
mg, 0.3 mmol), 4-methoxythiophenol (28.0 mg, 0.2 mmol), and
DIPEA (15.5 mg, 0.12 mmol) were irradiated in DMSO (2 mL) to
provide compound 8 (28.9 mg, 65%) as a yellow oil. The eluent was
petroleum ether. 1H NMR (500 MHz, CDCl3): δ 7.40−7.37 (m, 2H),
6.86−6.83 (m, 2H), 3.80 (s, 3H), 2.92−2.88 (m, 1H), 1.94−1.92 (m,
2H), 1.76−1.74 (m, 2H), 1.61−1.59 (m, 1H), 1.34−1.19 (m, 5H).
13C{1H} NMR (125 MHz, CDCl3): δ 159.3, 135.7, 124.9, 114.3, 55.3,
47.9, 33.4, 26.2, 25.8.
2-(Cyclohexylthio) Benzo[d]thiazole (9).20 This compound was
prepared by NHPI ester 1d (82.0 mg, 0.3 mmol) and 2-
mercaptobenzothiazole (33.4 mg, 0.2 mmol) with DIPEA (15.5 mg,
0.12 mmol) in DMSO (2 mL) under irradiation in 45.4 mg (91%)
yield as a yellow solid. The eluent was a 30/1 petroleum ether/ethyl
acetate mixture. 1H NMR (500 MHz, CDCl3): δ 7.88 (d, J = 7.8 Hz,
1H), 7.74 (d, J = 7.8 Hz, 1H), 7.40 (td, J = 7.8, 1.1 Hz, 1H), 7.28 (td,
J = 7.8, 1.1 Hz, 1H), 3.92−3.88 (m, 1H), 2.21−2.18 (m, 2H), 1.82−
1.78 (m, 2H), 1.66−1.55 (m, 3H), 1.51−1.43 (m, 2H), 1.37−1.25
(m, 1H). 13C{1H} NMR (125 MHz, CDCl3): δ 166.5, 153.4, 135.3,
125.9, 124.2, 121.6, 120.9, 47.3, 33.3, 25.8, 25.6.
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eluent was a 30/1 petroleum ether/ethyl acetate mixture. H NMR
(400 MHz, CDCl3): δ 7.40 (d, J = 8.3 Hz, 2H), 7.25−7.24 (m, 4H),
7.04 (d, J = 8.3 Hz, 2H), 3.10 (t, J = 7.6 Hz, 2H), 2.84 (t, J = 7.6 Hz,
2H). 13C{1H} NMR (100 MHz, CDCl3): δ 138.8, 134.6, 132.2, 131.6,
130.8, 130.3, 129.1, 120.4, 35.3, 34.9. HRMS (APCI) m/z: [M]+
calcd for C14H12ClBrS+ 325.9532, found 325.9533.
(4-Bromophenethyl)(4-bromophenyl) Sulfide (17). NHPI ester 1g
(112.3 mg, 0.3 mmol) and 4-bromothiophenol (37.8 mg, 0.2 mmol)
were irradiated with DIPEA (15.5 mg, 0.12 mmol) in DMSO (2 mL)
to provide compound 17 (61.0 mg, 82%) as a yellow oil. The eluent
2-(Cyclohexylthio) Pyridine (10).19 NHPI ester 1d (82.0 mg, 0.3
mmol) and 4-mercaptopyridine (22.2 mg, 0.2 mmol) were irradiated
in the presence of DIPEA (15.5 mg, 0.12 mmol) in DMSO (2 mL) to
obtain compound 10 (32.9 mg, 85%) as a yellow solid. The eluent
1
was a 30/1 petroleum ether/ethyl acetate mixture. H NMR (400
MHz, CDCl3): δ 7.41−7.38 (m, 4H), 7.19−7.17 (m, 2H), 7.04 (d, J =
8.3 Hz, 2H), 3.10 (t, J = 7.6 Hz, 2H), 2.85 (t, J = 7.6 Hz, 2H).
13C{1H} NMR (100 MHz, CDCl3): δ 138.8, 135.3, 132.0, 131.6,
130.9, 130.3, 120.4, 120.0, 35.1, 34.9. HRMS (APCI) m/z: [M]+
calcd for C14H12Br2S+ 369.9026, found 369.9027.
1
was a 30/1 petroleum ether/ethyl acetate mixture. H NMR (500
MHz, CDCl3): δ 8.39 (d, J = 5.8 Hz, 2H), 7.13 (d, J = 5.8 Hz, 2H),
3.38−3.33 (m, 1H), 2.08−2.05 (m, 2H), 1.81 (m, 2H), 1.66 (m, 1H),
1.48−1.31 (m, 5H). 13C{1H} NMR (125 MHz, CDCl3): δ 149.2,
148.7, 121.8, 43.4, 32.9, 25.9, 25.6.
(4-Chlorophenyl)[1-(4-isobutylphenyl)ethyl] Sulfide (18). NHPI
ester 1m (105.4 mg, 0.3 mmol), 4-chlorothiophenol (28.9 mg, 0.2
mmol), and DIPEA (15.5 mg, 0.12 mmol) in DMSO (2 mL) were
irradiated to afford compound 18 (22.6 mg, 37%) as a yellow oil. The
Cyclohexyl (Naphthalen-2-yl) Sulfide (11).3f Compound 11 was
prepared by NHPI ester 1d (82.0 mg, 0.3 mmol) and 2-
naphthalenethiol (32.0 mg, 0.2 mmol) in the presence of DIPEA
(15.5 mg, 0.12 mmol) to obtain 82% (39.7 mg) yield as a colorless oil.
The eluent was petroleum ether. 1H NMR (500 MHz, CDCl3): δ 7.85
(m, 1H), 7.79−7.73 (m, 3H), 7.48−7.41 (m, 3H), 3.22 (m, 1H),
2.04−2.00 (m, 2H), 1.80−1.76 (m, 2H), 1.64−1.60 (m, 1H), 1.45−
1.22 (m, 5H). 13C{1H} NMR (125 MHz, CDCl3): δ 133.7, 132.6,
132.1, 130.2, 129.6, 128.2, 127.7, 127.2, 126.4, 125.8, 46.5, 33.4, 26.0,
25.8.
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eluent was a 50/1 petroleum ether/ethyl acetate mixture. H NMR
(500 MHz, CDCl3): δ 7.16−7.14 (m, 6H), 7.05−7.03 (m, 2H), 4.28
(q, J = 6.9 Hz, 1H), 2.43 (d, J = 7.1 Hz, 2H), 1.83−1.80 (m, 1H),
1.61 (d, J = 6.9 Hz, 3H), 0.88 (d, J = 6.5 Hz, 1H). 13C{1H} NMR
(125 MHz, CDCl3): δ 140.8, 140.0, 134.1, 133.7, 133.4, 129.2, 128.8,
127.1, 48.1, 45.1, 30.2, 22.4, 22.1. HRMS (ESI) m/z: [M − H]− calcd
for C18H20ClS− 303.0980, found 303.0982.
tert-Butyl 2-[(4-Chlorophenyl)thio] Piperidine-1-carboxylate
(19). Compound 19 was prepared from NHPI ester 1h (112.3 mg,
0.3 mmol) and 4-chlorothiophenol (28.9 mg, 0.2 mmol) in the
presence of DIPEA (15.5 mg, 0.12 mmol) in DMSO (2 mL) under
irradiation in 80% (52.4 mg) yield as a yellow oil. The eluent was a
30/1 petroleum ether/ethyl acetate mixture. The product gives two
sets of NMR signals at an approximate ratio of 4/5, due to there being
conformational isomers of tertiary amines. 1H NMR (500 MHz,
CDCl3): δ 7.41 (m, 2H), 7.27−7.20 (m, 2H), 6.03−5.74 (m, 1H),
4.05−3.84 (m, 1H), 3.29−3.23 (td, J = 13.0, 2.6 Hz, 1H), 1.95 (m,
1H), 1.90−1.81 (m, 2H), 1.72−1.67 (m, 2H), 1.46−1.44 (m, 1H),
1.30 (s, 4H), 1.19 (s, 5H). 13C{1H} NMR (125 MHz, CDCl3): δ
154.0, 153.7, 136.3, 135.4, 134.4, 133.9, 132.3, 132.1, 129.2, 129.0,
80.1, 64.3, 62.0, 39.4, 38.0, 31.1, 30.3, 28.3, 28.0, 25.4, 19.8. HRMS
(ESI) m/z: [M + Na]+ calcd for C16H22ClNO2NaS+ 350.0952, found
350.0948.
4-(Naphthalen-2-ylthio)butan-2-one (12).21 This compound was
prepared by NHPI ester 1e (78.4 mg, 0.3 mmol) and 2-
naphthalenethiol (32.0 mg, 0.2 mmol) with DIPEA (15.5 mg, 0.12
mmol) in DMSO (2 mL) under irradiation in 67% (30.9 mg) yield as
an orange solid. The eluent was petroleum ether. 1H NMR (500
MHz, CDCl3): δ 7.80−7.74 (m, 4H), 7.49−7.40 (m, 3H), 3.23 (t, J =
7.3 Hz, 2H), 2.80 (t, J = 7.3 Hz, 2H), 2.14 (s, 3H). 13C{1H} NMR
(125 MHz, CDCl3): δ 206.6, 133.7, 133.1, 131.9, 128.6, 127.7, 127.5,
127.3, 127.1, 126.6, 125.8, 43.0, 30.1, 27.3.
4-[(4-Fluorophenyl)thio]butan-2-one (13).22 NHPI ester 1e (78.4
mg, 0.3 mmol) and 4-fluorothiophenol (25.6 mg, 0.2 mmol) were
irradiated in the presence of DIPEA (15.5 mg, 0.12 mmol) in DMSO
(2 mL) to afford compound 13 (34.1 mg, 86%) as a yellow oil. The
1
eluent was a 20/1 petroleum ether/ethyl acetate mixture. H NMR
(500 MHz, CDCl3): δ 7.37−7.34 (m, 2H), 7.02−6.99 (m, 2H), 3.08
(t, J = 7.3 Hz, 2H), 2.72 (t, J = 7.3 Hz, 2H), 2.14 (s, 3H). 13C{1H}
NMR (125 MHz, CDCl3): δ 206.5, 163.0, 161.0, 132.8, 132.7, 130.5,
116.2, 116.1, 43.1, 30.1, 28.9. 19F NMR (375 MHz, CDCl3): δ
−115.1.
tert-Butyl 3-[(4-Fluorophenyl)thio] Piperidine-1-carboxylate
(20). NHPI active ester 1i (112.3 mg, 0.3 mmol), 4-fluorothiophenol
(25.6 mg, 0.2 mmol), and DIPEA (15.5 mg, 0.12 mmol) in DMSO (2
mL) were irradiated to afford 20 (61.7 mg, 99%) as a yellow oil. The
1
eluent was a 20/1 petroleum ether/ethyl acetate mixture. H NMR
4-[(4-Chlorophenyl)thio]butan-2-one (14).23 NHPI ester 1e (78.4
mg, 0.3 mmol) and 4-chlorothiophenol (28.9 mg, 0.2 mmol) were
irradiated with DIPEA (15.5 mg, 0.12 mmol) in DMSO (2 mL) to
obtain compound 14 (32.6 mg, 76%) as a yellow solid. The eluent
(500 MHz, CDCl3): δ 7.44−7.41 (m, 2H), 7.02−6.99 (m, 2H), 4.04
(br, 1H), 3.87−3.85 (m, 1H), 3.10−2.98 (m, 1H), 2.86−2.79 (m,
2H), 2.08−2.05 (m, 1H), 1.77−1.73 (m, 1H), 1.53−1.44 (m, 2H),
1.41 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3): δ 163.4, 161.4,
154.4, 134.9, 128.7, 116.1, 116.0, 79.6, 49.6, 44.8, 43.9, 30.9, 28.4,
25.1. 19F NMR (375 MHz, CDCl3): δ −114.2. HRMS (ESI) m/z: [M
+ Na]+ calcd for C16H22FNO2NaS+ 334.1247, found 334.1243.
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was a 30/1 petroleum ether/ethyl acetate mixture. H NMR (500
MHz, DMSO-d6): δ 7.37 (d, J = 8.3 Hz, 2H), 7.33 (d, J = 8.3 Hz,
2H), 3.10 (t, J = 7.0 Hz, 2H), 2.77 (t, J = 7.0 Hz, 2H), 2.10 (s, 3H).
E
J. Org. Chem. XXXX, XXX, XXX−XXX