Journal of Agricultural and Food Chemistry
Article
([M + H]+): 596.1197. Found: 596.1194. [α]20 = −18.8 (c = 3,
(S,S)-3-Nitro-N2-(1-(N-cyano-S-methylsulfinimidoyl)propan-2-yl)-
N1-(2-methyl-4-(perfluoropropan-2-yl)phenyl)phthalamide, IId: white
solid; yield 30.2%; mp 99−102 °C; 1H NMR (400 MHz, DMSO-d6) δ
10.22 (s, 1H, Ar−NH), 8.88 (d, J = 7.1 Hz, 1H, −CNH), 8.26 (d, J =
7.7 Hz, 1H, Ar−H), 8.10 (d, J = 7.0 Hz, 1H, Ar−H), 7.84 (d, J = 7.6
Hz, 2H, Ar−H), 7.57 (m, 2H, Ar−H), 4.19 (m, 1H, −N−CH), 3.26−
3.18 (m, 1H, −SCH2), 3.14 (m, 1H, −SCH2), 2.68 (s, 3H, −SCH3),
2.40 (s, 3H, ArCH3), 1.25 (d, J = 5.7 Hz, 3H, −CCH3); 13C NMR
(101 MHz, DMSO-d6) δ 166.25, 164.84, 147.80, 140.27, 138.30,
134.77, 134.28, 132.31, 131.46, 128.43 (d, J = 10.5 Hz), 126.91 (d, J =
19.0 Hz), 124.47, 122.98 (d, J = 20.5 Hz), 121.07, 55.73, 42.53, 33.84,
20.60, 19.18. HRMS calcd for C23H20F7N5O4SH ([M + H]+):
D
MeOH).
(S,R)-3-Bromo-N2-(1-(N-cyano-S-methylsulfinimidoyl)propan-2-
yl)-N1-(2-methyl-4-(perfluoropropan-2-yl)phenyl)phthalamide, Ie:
white solid; yield 71.2%; mp 116−118 °C; 1H NMR (400 MHz,
DMSO-d6) δ 10.02 (s, 1H, Ar−NH), 8.89 (d, J = 8.0 Hz, 1H, −CNH),
7.85 (d, J = 8.0 Hz, 1H, Ar−H), 7.78 (dd, J = 13.7, 8.2 Hz, 2H, Ar−
H), 7.55 (d, J = 7.7 Hz, 2H, Ar−H), 7.51 (t, J = 7.9 Hz, 1H, Ar−H),
4.26 (dt, J = 13.7, 6.9 Hz, 1H, −N−CH), 3.30 (dd, J = 12.7, 5.9 Hz,
1H, −SCH2), 3.18 (dd, J = 12.7, 7.1 Hz, 1H, −SCH2), 2.69 (s, 3H,
−SCH3), 2.37 (s, 3H, ArCH3), 1.26 (d, J = 6.8 Hz, 3H, −CCH3); 13
C
NMR (101 MHz, DMSO-d6) δ 165.77, 165.31, 139.24, 137.80, 136.15,
134.60, 133.75, 130.36, 127.55−126.83 (m), 125.91, 123.32 (d, J =
10.2 Hz), 121.79 (d, J = 20.5 Hz), 121.59−121.53 (m), 120.47, 120.06,
118.98, 118.71, 54.80, 41.24, 31.95, 18.75, 17.96. HRMS calcd for
596.1197. Found: 596.1194. [α]20 = +23.6 (c = 2, MeOH).
D
(S,S)-3-Bromo-N2-(1-(N-cyano-S-methylsulfinimidoyl)propan-2-
yl)-N1-(2-methyl-4-(perfluoropropan-2-yl)phenyl)phthalamide, IIe:
white solid; yield 28.8%; mp 94−96 °C; 1H NMR (400 MHz,
DMSO-d6) δ 10.05 (d, J = 12.5 Hz, 1H, Ar−NH), 8.76 (t, J = 8.1 Hz,
1H, −CNH), 7.74−7.69 (m, 3H, Ar−H), 7.60−7.47 (m, 3H, Ar−H),
4.25 (m, 1H, −N−CH), 3.27−3.16 (m, 2H, −SCH2), 2.71 (d, J = 5.9
Hz, 3H, −SCH3), 2.37 (s, 3H, ArCH3), 1.25 (d, J = 6.7 Hz, 3H,
−CCH3); 13C NMR (101 MHz, DMSO) δ 165.61, 164.89, 139.28,
137.83, 136.34, 135.93, 134.43, 133.77, 131.32, 130.63, 130.17,
127.25−126.47 (m), 125.88, 123.35, 121.73 (d, J = 20.7 Hz),
121.53−121.35 (m), 120.06, 54.52, 41.07, 32.79 (d, J = 8.3 Hz), 19.74,
18.00. HRMS calcd for C23H20BrF7N4O2SH ([M + H]+): 629.0452.
C23H20BrF7N4O2SH ([M + H]+): 629.0452. Found: 629.0453. [α]20
D
= −4.0 (c = 1.5, MeOH).
(S,R)-N2-(1-(N-Cyano-S-methylsulfinimidoyl)propan-2-yl)-N1-(3-
(trifluoromethyl)phenyl)phthalamide, If: white solid; yield 79.7%; mp
74−78 °C; 1H NMR (400 MHz, DMSO-d6) δ 10.69 (s, 1H, Ar−NH),
8.75 (s, 1H, −CNH), 8.21 (s, 1H, Ar−H), 7.91 (d, J = 7.8 Hz, 1H,
Ar−H), 7.66−7.57 (m, 5H, Ar−H), 7.44 (d, J = 7.4 Hz, 1H, Ar−H),
4.35−4.25 (m, 1H, −N−CH), 3.38−3.36 (m, 1H, −SCH2), 3.29−3.21
(m, 1H, −SCH2), 2.83 (s, 3H, −SCH3), 1.29 (d, J = 5.6 Hz, 3H,
−CCH3); 13C NMR (101 MHz, DMSO-d6) δ 167.39, 167.34, 140.14,
136.33, 135.58, 129.92, 129.67 (d, J = 32.5 Hz), 129.20, 127.67 (d, J =
18.9 Hz), 125.49, 123.06, 122.78, 120.55, 119.69, 115.54, 55.35, 41.27,
32.24, 19.44. HRMS calcd for C20H19F3N4O2SH ([M + H]+),
Found: 629.0453. [α]20 = +2.6 (c = 0.5, MeOH).
D
(S,S)-N2-(1-(N-Cyano-S-methylsulfinimidoyl)propan-2-yl)-N1-(3-
(trifluoromethyl)phenyl)phthalamide, IIf: white solid; yield 20.3%; mp
85−87 °C; 1H NMR (400 MHz, DMSO-d6) δ 10.68 (s, 1H, Ar−NH),
8.58 (d, J = 7.2 Hz, 1H, −CNH), 8.20 (m, 1H, Ar−H), 7.89 (m, 1H,
Ar−H), 7.59 (d, J = 5.9 Hz, 5H, Ar−H), 7.44 (d, J = 7.2 Hz, 1H, Ar−
H), 4.27 (m, 1H, −N−CH), 3.29 (d, J = 9.6 Hz, 2H, −SCH2), 2.81 (s,
3H, −SCH3), 1.27 (d, J = 6.6 Hz, 3H, −CCH3); 13C NMR (101 MHz,
DMSO-d6) δ 167.43, 167.23, 140.17, 136.43, 135.62, 129.84 (d, J =
10.9 Hz), 129.50, 129.19, 127.70 (d, J = 23.9 Hz), 125.50, 123.05,
120.08, 119.63, 115.54, 54.24, 41.01, 32.67, 19.88. HRMS calcd for
437.1254. Found: 437.1252. [α]20 = −29.8 (c = 10, MeOH).
D
(S,S)-3-Iodo-N2-(1-(N-cyano-S-methylsulfinimidoyl)propan-2-yl)-
N1-(2-methyl-4-(perfluoropropan-2-yl)phenyl)phthalamide, IIa: white
solid; yield 29.7%; mp 116−118 °C; 1H NMR (400 MHz, DMSO-d6)
δ 9.96 (s, 1H, Ar−NH), 8.70 (d, J = 6.6 Hz, 1H, −CNH), 8.04 (d, J =
6.8 Hz, 1H, Ar−H), 7.82−7.74 (m, 2H, Ar−H), 7.55 (m, 2H, Ar−H),
7.31 (m, 1H, Ar−H), 4.23 (m, 1H, -N−CH), 3.28−3.20 (m, 1H,
−SCH2), 3.16 (d, J = 11.1 Hz, 1H, −SCH2), 2.67 (s, 3H, −SCH3),
2.37 (s, 3H, ArCH3), 1.28 (d, J = 5.1 Hz, 3H, −CCH3); 13C NMR
(101 MHz, DMSO-d6) δ 167.72, 165.51, 140.77, 141.58, 139.29,
135.86, 133.52, 130.29, 127.36, 125.67, 123.34, 121.50, 120.12, 95.101,
54.76, 41.15, 32.80, 19.62, 17.98. HRMS calcd for C23H20F7IN4O2SH
C20H19F3N4O2SH ([M + H]+): 437.1254. Found: 437.1252. [α]20
+45.1 (c = 10, MeOH).
=
D
(R,S)-3-Iodo-N2-(1-(N-cyano-S-methylsulfinimidoyl)propan-2-yl)-
N1-(2-methyl-4-(perfluoropropan-2-yl)phenyl)phthalamide, IIIa:
white solid; yield 70.3%; mp 116−118 °C; 1H NMR (400 MHz,
DMSO-d6) δ 9.95 (s, 1H, Ar−NH), 8.83 (d, J = 7.8 Hz, 1H, −CNH),
8.05 (d, J = 7.9 Hz, 1H, Ar−H), 7.79−7.75 (m, 2H, Ar−H), 7.54 (d, J
= 7.3 Hz, 2H, Ar−H), 7.31 (t, J = 7.8 Hz, 1H, Ar−H), 4.24 (dt, J =
13.6, 6.8 Hz, 1H, −N−CH), 3.29 (dd, J = 12.7, 5.9 Hz, 1H, −SCH2),
3.18 (dd, J = 7.9, 4.9 Hz, 1H, −SCH2), 2.66 (s, 3H, −SCH3), 2.36 (s,
3H, ArCH3), 1.26 (d, J = 6.7 Hz, 3H, −CCH3); 13C NMR (101 MHz,
DMSO-d6) δ 167.68, 165.45, 141.54, 140.92, 139.25, 135.59, 133.63,
130.31, 127.38, 127.20, 125.79, 123.33, 121.80, 120.48, 95.32, 54.77,
41.27, 32.01, 18.67, 17.94. Anal. Calcd for C23H20F7IN4O2S: C, 40.75;
H, 3.01; N, 8.13. Found: C, 40.84; H, 2.98; N, 8.28. HRMS calcd for
([M + H]+): 677.0313. Found: 677.0310. [α]20 = +51.2 (c = 10,
D
EtOAc).
(S,S)-3-Fluoro-N2-(1-(N-cyano-S-methylsulfinimidoyl)propan-2-
yl)-N1-(2-methyl-4-(perfluoropropan-2-yl)phenyl)phthalamide, IIb:
white solid; yield 40.4%; mp 106−107 °C; 1H NMR (400 MHz,
DMSO-d6) δ 10.11 (s, 1H, Ar−NH), 8.79 (d, J = 7.6 Hz, 1H, −CNH),
7.75 (d, J = 7.9 Hz, 1H, Ar−H), 7.61 (m, 2H, Ar−H), 7.54 (d, J = 9.2
Hz, 2H, Ar−H), 7.49 (d, J = 8.0 Hz, 1H, Ar−H), 4.27 (m, 1H, −N−
CH), 3.23 (m, 2H, −SCH2), 2.76 (s, 3H, −SCH3), 2.38 (s, 3H,
ArCH3), 1.27 (d, J = 6.4 Hz, 3H, −CCH3); 13C NMR (101 MHz,
DMSO-d6) δ 165.38, 163.01, 159.54, 159.09, 139.32, 136.98, 133.91,
130.92 (d, J = 32.0 Hz), 127.18 (d, J = 44.0 Hz), 126.09, 124.91 (d, J =
79.6 Hz), 123.28 (d, J = 37.6 Hz), 121.78 (d, J = 80.4 Hz), 119.91,
117.91 (d, J = 87.6 Hz), 54.48, 41.20, 32.67, 19.90, 18.00. HRMS calcd
C23H20F7IN4O2SH ([M + H]+): 677.0313. Found: 677.0310. [α]20
+8.3 (c = 10, EtOAc).
=
D
(R,S)-3-Fluoro-N2-(1-(N-cyano-S-methylsulfinimidoyl)propan-2-
yl)-N1-(2-methyl-4-(perfluoropropan-2-yl)phenyl)phthalamide, IIIb:
white solid; yield 59.6%; mp 106−108 °C; 1H NMR (400 MHz,
DMSO-d6) δ 10.13 (s, 1H, Ar−NH), 8.96 (d, J = 7.9 Hz, 1H, −CNH),
7.75 (d, J = 8.1 Hz, 1H, Ar−H), 7.64 (m, 2H, Ar−H), 7.56 (d, J = 8.3
Hz, 2H, Ar−H), 7.53−7.46 (m, 1H, Ar−H), 4.40−4.22 (m, 1H, −N−
CH), 3.43−3.27 (m, 1H, −SCH2), 3.20 (dd, J = 12.6, 6.9 Hz, 1H,
−SCH2), 2.74 (s, 3H, −SCH3), 2.39 (s, 3H, ArCH3), 1.28 (d, J = 6.6
Hz, 3H, −CCH3); 13C NMR (101 MHz, DMSO-d6) δ 165.31, 163.06,
159.62, 157.17, 139.28, 136.62, 134.00, 130.95, 127.25, 126.20, 123.80,
123.34, 120.43, 118.18, 117.95, 54.90, 32.07, 18.90, 17.98. HRMS
calcd for C23H20F8N4O2SH ([M + H]+): 569.1252. Found: 569.1256.
for C23H20F8N4O2SH ([M + H]+): 569.1252. Found: 569.1256. [α]20
D
= +42.0 (c = 10, EtOAc).
(S,S)-3-Chloro-N2-(1-(N-cyano-S-methylsulfinimidoyl)propan-2-
yl)-N1-(2-methyl-4-(perfluoropropan-2-yl)phenyl)phthalamide, IIc:
white solid; yield 38.8%; mp 83−86 °C; 1H NMR (400 MHz,
DMSO-d6) δ 10.05 (s, 1H, Ar−NH), 8.76 (d, J = 7.8 Hz, 1H, −CNH),
7.76 (dd, J = 14.4, 7.9 Hz, 2H, Ar−H), 7.70 (d, J = 7.9 Hz, 1H, Ar−
H), 7.61−7.53 (m, 3H, Ar−H), 4.26 (m, 1H, −N−CH), 3.22 (m, 2H,
−SCH2), 2.72 (s, 3H, −SCH3), 2.38 (s, 3H, ArCH3), 1.26 (d, J = 6.7
Hz, 3H, −CCH3); 13C NMR (101 MHz, DMSO-d6) δ 165.38, 164.88,
139.26, 136.32, 135.91, 133.76, 131.31, 130.62, 130.16, 127.19 (d, J =
11.2 Hz), 126.46, 125.87, 123.35, 121.83, 121.63, 120.04, 54.53, 41.06,
32.75, 19.73, 17.99. Aanl. Calcd for C23H20ClF7N4O2S: C, 47.23; H,
3.45; N, 9.58. Found: C, 46.98; H, 3.48; N, 9.68. HRMS calcd for
[α]20 = +30.9 (c = 10, EtOAc).
D
(R,S)-3-Chloro-N2-(1-(N-cyano-S-methylsulfinimidoyl)propan-2-
yl)-N1-(2-methyl-4-(perfluoropropan-2-yl)phenyl)phthalamide, IIIc:
white solid; yield 61.2%; mp 121−122 °C; 1H NMR (300 MHz,
DMSO-d6) δ 10.05 (s, 1H, Ar−NH), 8.91 (s, 1H, −CNH), 7.72 (m,
C23H20ClF7N4O2SH ([M + H]+): 585.0957. Found: 585.0951. [α]20
D
= +68.4 (c = 10, MeOH).
6271
dx.doi.org/10.1021/jf501727k | J. Agric. Food Chem. 2014, 62, 6269−6277