Page 9 of 14
The Journal of Organic Chemistry
4
-(Benzo[d]thiazol-2-ylthio)pentanenitrile (3ab). Colorless oil;
7.02 (dd, J = 8.9, 2.5 Hz, 1H), 4.11 (dddd, J = 9.9, 8.0, 6.0, 4.1 Hz,
1H), 3.85 (s, 3H), 3.29 (dd, J = 14.0, 6.2 Hz, 1H), 2.97 (dd, J = 14.0,
8.3 Hz, 1H), 2.68 – 2.47 (m, 2H), 2.25 – 2.14 (m, 1H), 2.02 (dtd, J =
1
1
isolated yield = 79%, 39.0 mg; H NMR (400 MHz, Chloroform-d) δ
7.87 (d, J = 8.4 Hz, 1H), 7.74 (dd, J = 7.8, 1.3 Hz, 1H), 7.41 (ddd, J =
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
14.6, 8.9, 5.9 Hz, 1H). 13C{ H} NMR (101 MHz, Chloroform-d) δ
1
8
.3, 7.2, 1.3 Hz, 1H), 7.30 (ddd, J = 8.3, 7.3, 1.2 Hz, 1H), 4.16 – 4.01
(m, 1H), 2.66 – 2.48 (m, 2H), 2.23 – 2.08 (m, 2H), 1.53 (d, J = 7.0
160.8, 157.3, 147.7, 137.6, 136.8, 129.3, 128.7, 127.0, 122.4, 119.2,
Hz, 3H). 13C{ H} NMR (101 MHz, Chloroform-d) δ 164.6, 153.1,
1
115.1, 103.9, 55.8, 49.5, 41.4, 29.6, 15.2. HRMS (ESI-TOF) m/z:
+
1
35.3, 126.2, 124.6, 121.8, 121.0, 119.2, 42.8, 32.5, 21.0, 15.1.
[M+H] calcd for C19
H
19
N
2
OS
2
355.0933; Found: 355.0935.
HRMS (ESI-TOF) m/z: [M+H]+ calcd for C12
H N S 249.0515;
13 2 2
4
-((6-Bromobenzo[d]thiazol-2-yl)thio)-5-phenylpentanenitrile (3cc).
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Found: 249.0518.
1
Pale yellow oil; isolated yield = 32%, 26.1 mg; H NMR (400 MHz,
Chloroform-d) δ 7.87 (d, J = 2.0 Hz, 1H), 7.73 (d, J = 8.6 Hz, 1H),
7.52 (dd, J = 8.6, 2.0 Hz, 1H), 7.43 – 7.03 (m, 5H), 4.24 (tdd, J = 8.3,
6.4, 4.2 Hz, 1H), 3.29 (dd, J = 14.0, 6.3 Hz, 1H), 3.00 (dd, J = 14.0,
8.2 Hz, 1H), 2.64 – 2.47 (m, 2H), 2.28 – 2.17 (m, 1H), 2.11 – 1.99 (m,
1H). 13C{ H} NMR (101 MHz, Chloroform-d) δ 165.4, 151.9, 137.4,
4
-(Thiazol-2-ylthio)pentanenitrile (3gb). Pale yellow oil; isolated
1
yield = 66%, 26.3 mg; H NMR (400 MHz, Chloroform-d) δ 7.71 (d,
J = 3.4 Hz, 1H), 7.28 (d, J = 3.4 Hz, 1H), 3.70 (h, J = 6.9 Hz, 1H),
2
.67 – 2.48 (m, 2H), 2.09 – 2.00 (m, 2H), 1.45 (d, J = 6.8 Hz, 3H).
1
3
1
1
C{ H} NMR (101 MHz, Chloroform-d) δ 161.3, 143.3, 120.6,
1
19.2, 43.8, 32.2, 21.0, 15.0. HRMS (ESI-TOF) m/z: [M+H]+ calcd
136.9, 129.6, 129.2, 128.7, 127.1, 123.5, 122.8, 119.1, 118.0, 49.4,
41.3, 29.6, 15.2. HRMS (ESI-TOF) m/z: [M+H]+ calcd for
for C
8 11 2 2
H N S 199.0358; Found: 199.0358.
18 2 2
C H16BrN S 402.9933; Found: 402.9932.
4
-((4,5-Dihydrothiazol-2-yl)thio)pentanenitrile (3hb). Colorless oil;
1
isolated yield = 72%, 28.8 mg; H NMR (400 MHz, Chloroform-d) δ
4-(Benzo[d]oxazol-2-ylthio)-5-phenylpentanenitrile (3ic). Colorless
oil; isolated yield
61%, 37.4 mg; 1H NMR (400 MHz,
4
2
3
4
.18 (t, J = 8.0 Hz, 2H), 3.82 (h, J = 7.0 Hz, 1H), 3.35 (t, J = 8.0 Hz,
H), 2.47 (t, J = 7.6 Hz, 2H), 2.08 – 1.96 (m, 2H), 1.40 (d, J = 7.0 Hz,
H). 13C{ H} NMR (101 MHz, Chloroform-d) δ 164.1, 119.3, 64.3,
=
Chloroform-d) δ 7.61 (dd, J = 7.3, 1.7 Hz, 1H), 7.44 (dd, J = 7.4, 1.7
Hz, 1H), 7.41 – 7.08 (m, 7H), 4.13 – 4.04 (m, 1H), 3.30 (dd, J = 14.0,
6.5 Hz, 1H), 3.05 (dd, J = 14.0, 8.1 Hz, 1H), 2.65 – 2.48 (m, 2H), 2.30
– 2.20 (m, 1H), 2.11 (dtd, J = 14.7, 8.9, 5.9 Hz, 1H). 13C{ H} NMR
1
+
1.7, 35.3, 32.5, 20.9, 14.9. HRMS (ESI-TOF) m/z: [M+H] calcd for
1
8 13 2 2
C H N S 201.0515; Found: 201.0513.
(
101 MHz, Chloroform-d) δ 162.8, 151.7, 141.7, 137.3, 129.3, 128.7,
4-(Benzo[d]oxazol-2-ylthio)pentanenitrile (3ib). Colorless oil;
1
127.2, 124.5, 124.3, 119.0, 118.7, 110.0, 48.5, 41.2, 29.5, 15.2.
isolated yield = 88%, 40.8 mg; H NMR (400 MHz, Chloroform-d) δ
HRMS (ESI-TOF) m/z: [M+H]+ calcd for C18
H N OS 309.1056;
17 2
7
.57 (d, J = 6.8 Hz, 1H), 7.50 – 7.35 (m, 1H), 7.35 – 7.15 (m, 2H),
Found: 309.1057.
3.95 (h, J = 7.0 Hz, 1H), 2.56 (t, J = 7.3 Hz, 2H), 2.26 – 2.10 (m, 2H),
.56 (d, J = 7.0 Hz, 3H). 13C{ H} NMR (101 MHz, Chloroform-d) δ
1
4-(Benzo[d]thiazol-2-ylthio)-3-phenylbutanenitrile (3ad). Colorless
oil; isolated yield
74%, 45.7 mg; 1H NMR (400 MHz,
1
1
2
63.0, 151.6, 141.7, 124.4, 124.2, 119.0, 118.6, 110.0, 42.0, 32.2,
=
1.1, 15.0. HRMS (ESI-TOF) m/z: [M+H]+ calcd for C12
H
13
N
2
OS
Chloroform-d) δ 7.89 (d, J = 8.1 Hz, 1H), 7.75 (d, J = 7.9 Hz, 1H),
233.0743; Found: 233.0747.
7.52 – 7.26 (m, 7H), 3.73 (d, J = 7.3 Hz, 2H), 3.56 (p, J = 7.4 Hz,
1
H), 2.95 – 2.81 (m, 2H). 13C{ H} NMR (101 MHz, Chloroform-d) δ
1
4
-(Benzo[d]thiazol-2-ylthio)-5-phenylpentanenitrile (3ac). Colorless
48%, 30.9 mg; 1H NMR (400 MHz,
oil; isolated yield
Chloroform-d) δ 7.90 (d, J = 8.1 Hz, 1H), 7.75 (d, J = 8.0 Hz, 1H),
165.2, 152.9, 139.7, 135.3, 129.1, 128.2, 127.3, 126.2, 124.5, 121.6,
=
+
121.1, 118.0, 41.7, 37.7, 23.3. HRMS (ESI-TOF) m/z: [M+K] calcd
14 2 2
for C17H N S K 349.0230; Found: 349.0224.
7
6
8
.46 – 7.40 (m, 1H), 7.38 – 7.18 (m, 6H), 4.23 (dddd, J = 10.1, 8.4,
.2, 4.1 Hz, 1H), 3.31 (dd, J = 14.0, 6.2 Hz, 1H), 2.99 (dd, J = 14.0,
4-((6-Methoxybenzo[d]thiazol-2-yl)thio)-3-phenylbutanenitrile
1
.3 Hz, 1H), 2.64 – 2.47 (m, 2H), 2.22 (dddd, J = 13.1, 8.8, 7.1, 4.2
(3bd). Colorless oil; isolated yield = 70%, 47.7 mg; H NMR (400
Hz, 1H), 2.05 (dtd, J = 14.6, 8.9, 5.9 Hz, 1H). 13C{ H} NMR (101
MHz, Chloroform-d) δ 164.5, 153.1, 137.6, 135.3, 129.3, 128.7,
127.1, 126.2, 124.6, 121.8, 121.0, 119.2, 49.2, 41.3, 29.6, 15.2.
1
MHz, Chloroform-d) δ 7.77 (d, J = 8.9 Hz, 1H), 7.45 – 7.27 (m, 5H),
7.22 (d, J = 2.5 Hz, 1H), 7.02 (dd, J = 8.9, 2.6 Hz, 1H), 3.84 (s, 3H),
3.75 – 3.62 (m, 2H), 3.53 (qd, J = 7.6, 5.3 Hz, 1H), 2.95 – 2.80 (m,
2H). 13C{ H} NMR (101 MHz, Chloroform-d) δ 161.9, 157.2, 147.5,
139.8, 136.7, 129.1, 128.1, 127.3, 122.1, 118.0, 115.0, 104.1, 55.8,
41.7, 37.9, 23.3. HRMS (ESI-TOF) m/z: [M+H]+ calcd for
HRMS (ESI-TOF) m/z: [M+H]+ calcd for C18
H
17
N
2
S
2
325.0828;
1
Found: 325.0828.
4
-((6-Methoxybenzo[d]thiazol-2-yl)thio)-5-phenylpentanenitrile
1
18 17 2 2
C H N OS 341.0777; Found: 341.0774.
(3bc). Colorless oil; isolated yield = 47%, 33.1 mg; H NMR (400
MHz, Chloroform-d) δ 7.79 (d, J = 8.9 Hz, 1H), 7.52 – 7.12 (m, 6H),
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