Access to N-Alkynylated Sulfonimidamides
4
-[S-Phenyl-NЈ-(3-chlorophenylethynyl)sulfonimidoyl]morpholine
alkyne); m.p. 101–103 °C. IR (ATR): ν˜ = 2965, 2910, 2204, 1342,
–
1 1
(3c): Pale yellow sticky liquid (16.7 mg, 79%; from 0.05882 mmol 1250, 1103 cm . H NMR (400 MHz, CDCl ): δ = 7.79 (d, J =
3
of terminal alkyne). IR (ATR): ν˜ = 2958, 2924, 2856, 2207, 1446,
8.32 Hz, 2 H), 7.36 (d, J = 8.20 Hz, 2 H), 7.18–7.10 (m, 3 H), 7.99
–1 1
1
2
1
3
1
5
112 cm . H NMR (400 MHz, CDCl
H), 7.68 (t, J = 7.32 Hz, 1 H), 7.59 (t, J = 7.96 Hz, 2 H), 7.31 (s,
3
): δ = 7.92 (d, J = 7.40 Hz, (d, J = 7.20 Hz, 1 H), 3.80–3.77 (m, 4 H), 3.13–3.10 (m, 4 H), 2.44
1
3
(s, 3 H), 2.29 (s, 3 H) ppm. C NMR (100 MHz, CDCl
3
): δ =
H), 7.23–7.20 (m, 1 H), 7.15–7.14 (m, 2 H), 3.81–3.79 (m, 4 H),
144.7, 137.6, 132.0, 130.3, 129.9, 128.4, 128.2, 128.0, 127.0, 125.5,
.15–3.13 (m, 4 H) ppm. 13C NMR (100 MHz, CDCl
): δ = 133.9, 85.7, 66.2, 59.2, 46.4, 21.6, 21.3 ppm. HRMS (ESI): calcd. for
33.3, 131.2, 129.5, 129.4, 129.3, 128.2, 127.5, 126.4, 87.3, 66.3,
S [M + H]+ 355.1474; found 355.1464.
8.3, 46.5 ppm. HRMS (ESI): calcd. for C18 17ClN S [M +
3
20 22 2 2
C H N O
H
2 2
O
4
-[S-p-Tolyl-NЈ-(3-chlorophenylethynyl)sulfonimidoyl]morpholine
3j): White solid (16.0 mg, 73%; from 0.05882 mmol of terminal
alkyne); m.p. 110–112 °C. IR (ATR): ν˜ = 2963, 2855, 2203, 1451,
+
H] 361.0772; found 361.0764.
-[S-Phenyl-NЈ-(3-methylphenylethynyl)sulfonimidoyl]morpholine
3d): Pale yellow sticky liquid (17.7 mg, 74%; from 0.06897 mmol
of terminal alkyne). IR (ATR): ν˜ = 3069, 2963, 2866, 2213, 1446,
(
4
(
–1 1
1
243, 1111 cm . H NMR (400 MHz, CDCl
3
): δ = 7.79 (d, J =
8.36 Hz, 2 H), 7.38 (d, J = 8.16 Hz, 2 H), 7.30 (s, 1 H), 7.21–7.19
–1 1
1
251, 1112 cm . H NMR (400 MHz, CDCl
3
): δ = 7.92 (d, J =
(
m, 1 H), 7.15–7.13 (m, 2 H), 3.80–3.78 (m, 4 H), 3.13–3.10 (m, 4
7.32 Hz, 2 H), 7.67 (t, J = 7.32 Hz, 1 H), 7.58 (t, J = 7.32 Hz, 2
13
H), 2.46 (s, 3 H) ppm. C NMR (100 MHz, CDCl
1
6
3
): δ = 145.0,
33.8, 131.2, 130.2, 130.1, 129.5, 129.3, 128.3, 127.6, 126.3, 87.6,
6 . 3 , 5 8 . 1 , 4 6 . 4 , 2 1 . 7 p p m . H R M S ( E S I ) : c a l c d . fo r
S [M + H]+ 375.0928; found 375.0921.
19ClN
H), 7.18–7.11 (m, 3 H), 6.99 (d, J = 6.96 Hz, 1 H), 3.81–3.78 (m,
H), 3.16–3.13 (m, 4 H), 2.29 (s, 3 H) ppm. 13C NMR (100 MHz,
CDCl ): δ = 137.7, 133.7, 133.6, 132.1, 129.4, 128.5, 128.2, 128.0,
27.1, 125.4, 85.4, 66.3, 59.5, 46.5, 21.3 ppm. HRMS (ESI): calcd.
4
3
C
19
H
2 2
O
1
+
4-[S-p-Tolyl-NЈ-(4-methoxyphenylethynyl)sulfonimidoyl]morpholine
3k): White solid (17.2 mg, 77%; from 0.06061 mmol of terminal
alkyne); m.p. 166–168 °C. IR (ATR): ν˜ = 2959, 2856, 2202, 1457,
for C19
-[S-Phenyl-NЈ-(4-methoxyphenylethynyl)sulfonimidoyl]morpholine
3e): White solid (16.8 mg, 78%; from 0.06061 mmol of terminal
alkyne); m.p. 125–127 °C. IR (ATR): ν˜ = 2957, 2860, 2205, 1448,
20 2 2
H N O S [M + H] 341.1318; found 341.1300.
(
4
(
–1 1
1
336, 1240, 1111 cm . H NMR (400 MHz, CDCl
3
): δ = 7.79 (d,
J = 8.08 Hz, 2 H), 7.36 (d, J = 8.20 Hz, 2 H), 7.28 (d, J = 8.68 Hz,
–1 1
1236, 1107 cm . H NMR (400 MHz, CDCl
3
): δ = 7.92 (d, J =
2
4
1
4
H), 6.78 (d, J = 8.68 Hz, 2 H), 3.80–3.77 (m, 7 H), 3.13–3.10 (m,
7.72 Hz, 2 H), 7.66 (t, J = 7.32 Hz, 1 H), 7.58 (t, J = 7.92 Hz, 2
13
H), 2.45 (s, 3 H) ppm. C NMR (100 MHz, CDCl
44.7, 132.7, 130.5, 130.0, 128.3, 117.9, 113.8, 84.2, 66.4, 58.8, 55.4,
6.5. 21.7 ppm. HRMS (ESI): calcd. for C20 S [M + H
3
): δ = 158.2,
H), 7.29 (d, J = 8.68 Hz, 2 H), 6.79 (d, J = 8.68 Hz, 2 H), 3.81–3.78
1
3
(
=
5
H
m, 7 H), 3.16–3.12 (m, 4 H) ppm. C NMR (100 MHz, CDCl
158.3, 133.8, 133.7, 132.8, 129.4, 128.3, 117.9, 113.9, 84.1, 66.4,
9.0, 55.4, 46.6 ppm. HRMS (ESI): calcd. for C19 S [M +
3
): δ
H
22
N
2
O
3
2
O
+
+
H] 389.1529; found 389.1536.
20 2 3
H N O
O + H]+ 375.1373; found 375.1383.
4-[S-p-Nitrophenyl-NЈ-(4-methoxyphenylethynyl)sulfonimidoyl]-
morpholine (3l): Yellow solid (24.4 mg, 84%; from 0.07843 mmol of
terminal alkyne); m.p. 162–163 °C. IR (ATR): ν˜ = 3102, 2905,
2
1
-[S-Phenyl-NЈ-(3-phenylethynyl)sulfonimidoyl]piperidine (3f):
Brown sticky liquid (13.4 mg, 53%; from 0.07843 mmol of terminal
–
1 1
2
851, 2207, 1349, 1247, 1111 cm . H NMR (400 MHz, CDCl
δ = 8.42 (d, J = 8.76 Hz, 2 H), 8.12 (d, J = 8.76 Hz, 2 H), 7.36–
.34 (m, 2 H), 7.27–7.20 (m, 3 H), 3.84–3.80 (m, 4 H), 3.22–3.19
3
):
alkyne). IR (ATR): ν˜ = 3060, 2925, 2852, 2200, 1446, 1243,
–
1 1
1
2
117 cm . H NMR (400 MHz, CDCl
3
): δ = 7.92 (d, J = 7.32 Hz,
7
(
1
H), 7.63 (t, J = 7.40 Hz, 1 H), 7.55 (t, J = 7.80 Hz, 2 H), 7.34
1
3
m, 4 H) ppm. C NMR (100 MHz, CDCl
31.5, 129.4, 128.3, 126.7, 125.0, 124.6, 84.3, 66.3, 60.3, 46.5 ppm.
HRMS (ESI): calcd. for C18
S [M + H]+ 372.1012; found
72.1005.
3
): δ = 150.8, 140.1,
(
7
(
1
2
3
d, J = 7.00 Hz, 2 H), 7.22 (t, J = 7.08 Hz, 2 H), 7.15 (t, J =
.36 Hz, 1 H), 3.18–3.14 (m, 4 H), 1.73–1.68 (m, 4 H), 1.49–1.46
m, 2 H) ppm. 13C NMR (100 MHz, CDCl
): δ = 135.0, 133.2,
31.4, 129.2, 128.1, 128.0, 126.1, 125.9, 86.7, 59.0, 47.4, 25.5,
17 3 4
H N O
3
3
3.7 ppm. HRMS (ESI): calcd. for C19
25.1369; found 325.1385.
H
20
N
2
OS [M + H]+
4-[S-p-Nitrophenyl-NЈ-(3-methylphenylethynyl)sulfonimidoyl]-
morpholine (3m): Brown sticky liquid (21.5 mg, 81 %; from
0
2
.06897 mmol of terminal alkyne). IR (ATR): ν˜ = 3102, 2919, 2857,
216, 1529, 1346, 1255, 1112 cm . H NMR (400 MHz, CDCl ):
3
4
-[S-p-Tolyl-NЈ-(phenylethynyl)sulfonimidoyl]morpholine (3g):
–
1 1
White solid (21.9 mg, 82%; from 0.07843 mmol of terminal alk-
yne); m.p. 120–121 °C. IR (ATR): ν˜ = 2963, 2856, 2206, 1349,
δ = 8.43 (d, J = 8.84 Hz, 2 H), 8.14 (d, J = 8.80 Hz, 2 H), 7.19–
7.16 (m, 3 H), 7.05–7.03 (m, 1 H), 3.85–3.82 (m, 4 H), 3.24–3.21
–1
1
1
2
7
3
249 cm . H NMR (400 MHz, CDCl ): δ = 7.78 (d, J = 8.32 Hz,
1
3
(
1
m, 4 H), 2.32 (s, 3 H) ppm. C NMR (100 MHz, CDCl
50.7, 140.1, 137.9, 132.1, 129.4, 128.6, 128.2, 127.6, 124.8, 124.6,
83.9, 66.3, 60.4, 46.5, 21.4 ppm. HRMS (ESI): calcd. for
S [M + H]+ 386.1169; found 386.1153.
3
): δ =
H), 7.36–7.32 (m, 4 H), 7.22 (t, J = 7.2 Hz, 2 H), 7.15 (t, J =
.2 Hz, 1 H), 3.79–3.76 (m, 4 H), 3.13–3.09 (m, 4 H), 2.44 (s, 3 H)
13
ppm. C NMR (100 MHz, CDCl
3
): δ = 144.8, 131.4, 130.4, 130.0,
19 19 3 4
C H N O
128.3, 128.1, 126.1, 125.7, 86.1, 66.3, 59.2, 46.4, 21.7 ppm. HRMS
+
(ESI): calcd. for C19
H
20
N
2
O
2
S [M + H] 341.1318; found 341.1324.
4-{S-Phenyl-NЈ-[tert-butyldimethyl(prop-2-ynyloxy)silane]sulfon-
imidoyl}morpholine (3n): Pale yellow sticky liquid (10.8 mg, 58%;
from 0.04734 mmol of terminal alkyne). IR (ATR): ν˜ = 2955, 2895,
4
-[S-p-Tolyl-NЈ-(p-tolylethynyl)sulfonimidoyl]morpholine (3h):
White solid (17.3 mg, 71%; from 0.06897 mmol of terminal alk-
yne); m.p. 115–117 °C. IR (ATR): ν˜ = 2960, 2918, 2201, 1347, 1244,
–
1 1
2
228, 1461, 1236, 1113 cm . H NMR (400 MHz, CDCl
7.86 (d, J = 7.56 Hz, 2 H), 7.64 (t, J = 7.48 Hz, 1 H), 7.55 (t, J =
.92 Hz, 2 H), 4.42 (s, 2 H), 3.78–3.75 (m, 4 H), 3.08–3.06 (m, 4
3
): δ =
–1 1
1
2
109 cm . H NMR (400 MHz, CDCl
3
): δ = 7.79 (d, J = 8.28 Hz,
7
H), 7.36 (d, J = 8.2 Hz, 2 H), 7.25 (d, J = 7.88 Hz, 2 H), 7.04 (d,
1
3
H), 0.98 (s, 9 H), 0.12 (s, 3 H), 0.11 (s, 3 H) ppm. C NMR
(100 MHz, CDCl ): δ = 133.6, 133.4, 129.3, 128.2, 80.3, 66.2, 56.9,
J = 7.88 Hz, 2 H), 3.80–3.77 (m, 4 H), 3.14–3.10 (m, 4 H), 2.45 (s,
H), 2.31 (s, 3 H) ppm. 1 C NMR (100 MHz, CDCl
3
3
1
2
3
3
): δ = 144.8,
3
52.6, 46.4, 26.0, 18.4, –4.77 ppm. HRMS (ESI): calcd. for
36.0, 131.3, 130.5, 130.0, 128.9, 128.3, 122.6, 85.1, 66.4, 59.2, 46.5,
1.7, 21.4 ppm. HRMS (ESI): calcd. for C20
55.1474; found 355.1458.
+
H
22
N
2
O
2
S [M + H]+
C H N O SSi [M + H] 395.1819; found 395.1821.
19 30
2
3
4
-[S-Phenyl-NЈ-(oct-1-ynyl)sulfonimidoyl]morpholine (3o): Pale yel-
4
-[S-p-Tolyl-NЈ-(3-methylphenylethynyl)sulfonimidoyl]morpholine low sticky liquid (13.7 mg, 56%; from 0.07339 mmol of terminal
alkyne). IR (ATR): ν˜ = 3102, 2919, 2857, 2216, 1529, 1346, 1255,
(3i): White solid (16.8 mg, 69%; from 0.06897 mmol of terminal
Eur. J. Org. Chem. 2015, 2861–2867
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2865