The Journal of Organic Chemistry
Note
N1,N1-Diisopropyl-N2-(4-methylbenzenesulfonyl)-2-(4-
8.2 Hz, 2H), 7.29−7.20 (m, 4H), 7.04−6.98 (m, 2H), 4.36 (s, 2H),
4.06 (p, J = 6.6 Hz, 1H), 3.55−3.36 (m, 1H), 2.39 (s, 3H), 1.37 (d, J =
6.8 Hz, 6H), 0.93 (d, J = 6.6 Hz, 6H); 13C NMR (101 MHz, CDCl3) δ
163.1, 141.6, 141.5, 134.4, 129.0, 127.8, 126.2, 126.1, 121.9, 50.5, 48.1,
33.8, 21.5, 19.9, 19.8; IR (neat) ν 1543, 1263, 1082, 1051, 807, 778,
669 cm−1; EMM (ESI, TOF) calc. for C19H27N2O2S2 [M + H]+
379.1509, found 379.1501.
trifluoromethylphenyl)acetamidine (4g).5 White solid: 132 mg,
1
99% of yield; mp 106−107 °C; H NMR (400 MHz, CDCl3) δ 7.79
(d, J = 8.4 Hz, 2H), 7.54 (d, J = 8.1 Hz, 2H), 7.33 (d, J = 8.0 Hz, 2H),
7.22 (d, J = 8.0 Hz, 2H), 4.48 (s, 2H), 3.91 (p, J = 6.6 Hz, 1H), 3.60−
3.36 (m, 1H), 2.38 (s, 3H), 1.40 (d, J = 6.7 Hz, 6H), 0.91 (d, J = 6.6
Hz, 6H); 13C NMR (101 MHz, CDCl3) δ 162.3, 141.9, 141.1, 139.1,
129.1 (q, J2 = 32.6 Hz), 129.1, 128.3, 126.2, 125.8 (q, J3 = 3.8 Hz),
124.1 (q, J1 = 272.9 Hz), 50.5, 48.2, 38.2, 21.4, 19.9, 19.8; IR (neat) ν
1543, 1323, 1254, 1077, 1051, 810, 744, 665 cm−1; EMM (ESI, TOF)
calc. for C22H28F3N2O2S [M + H]+ 441.1819, found 441.1833.
N1,N1-Diisopropyl-N2-(4-methylbenzenesulfonyl)-2-(3-
methylphenyl)acetamidine (4h). White solid: 108 mg, 93% of
N1,N1-Diisopropyl-N2-(4-methylbenzenesulfonyl)-2-
(cyclohexenyl)acetamidine (4n).5 White solid: 53 mg, 47% of
yield; mp 80−81 °C; 1H NMR (400 MHz, CDCl3) δ 7.78 (d, J = 8.3
Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 5.22 (dt, J = 3.8, 1.9 Hz, 1H), 3.94
(p, J = 6.6 Hz, 1H), 3.57 (d, J = 2.6 Hz, 2H), 3.54−3.43 (m, 1H), 2.38
(s, 3H), 2.02−1.83 (m, 4H), 1.64−1.55 (m, 2H), 1.53−1.44 (m, 2H),
1.40 (d, J = 6.8 Hz, 6H), 1.14 (d, J = 6.6 Hz, 6H); 13C NMR (101
MHz, CDCl3) δ 163.8, 141.7, 141.3, 131.2, 128.9, 126.3, 123.3, 50.2,
48.0, 39.8, 28.5, 25.2, 22.7, 22.0, 21.4, 20.3, 20.1; IR (neat) ν 1541,
1446, 1371, 1266, 1133, 1083, 1052, 811, 793, 666 cm−1; EMM (ESI,
TOF) calc. for C21H33N2O2S [M + H]+ 377.2258, found 377.2265.
N1,N1-Diisopropyl-N2-(4-methylbenzenesulfonyl)-(5-chloro)-
pentanamidine (4o).5 White solid: 76 mg, 68% of yield; mp 91−92
°C; 1H NMR (400 MHz, CDCl3) δ 7.80 (d, J = 8.2 Hz, 2H), 7.25 (d, J
= 8.0 Hz, 2H), 4.07 (p, J = 6.6 Hz, 1H), 3.62−3.52 (m, 3H), 3.02−
2.83 (m, 2H), 2.39 (s, 3H), 2.02−1.68 (m, 4H), 1.32 (d, J = 6.7 Hz,
6H), 1.24 (d, J = 6.6 Hz, 6H); 13C NMR (101 MHz, CDCl3) δ 165.5,
141.7, 141.5, 129.1, 126.0, 50.1, 48.0, 44.4, 32.0, 31.8, 24.2, 21.5, 20.7,
20.0; IR (neat) ν 1538, 1445, 1372, 1255, 1128, 1080, 1050, 821, 807,
792, 688 cm−1; EMM (ESI, TOF) calc. for C18H30ClN2O2S [M + H]+
373.1712, found 373.1711.
1
yield; mp 114−115 °C; H NMR (400 MHz, CDCl3) δ 7.81 (d, J =
8.3 Hz, 2H), 7.20 (d, J = 8.0 Hz, 2H), 7.15 (t, J = 7.6 Hz, 1H), 6.99 (d,
J = 7.5 Hz, 1H), 6.95 (d, J = 7.7 Hz, 1H), 6.90 (s, 1H), 4.36 (s, 2H),
3.98 (p, J = 6.6 Hz, 1H), 3.52−3.35 (m, 1H), 2.37 (s, 3H), 2.27 (s,
3H), 1.40 (d, J = 6.8 Hz, 6H), 0.88 (d, J = 6.6 Hz, 6H); 13C NMR
(101 MHz, CDCl3) δ 163.6, 141.5, 141.5, 138.3, 134.7, 129.0, 128.7,
128.6, 127.4, 126.3, 124.9, 50.4, 48.0, 38.3, 21.4, 21.4, 19.9, 19.8; IR
(neat) ν 1538, 1451, 1372, 1261, 1137, 1084, 1048, 952, 909, 825, 782,
731, 696, 660 cm−1; EMM (ESI, TOF) calc. for C22H31N2O2S [M +
H]+ 387.2101, found 387.2094.
N1,N1-Diisopropyl-N2-(4-methylbenzenesulfonyl)-2-(3-
acetylphenyl)acetamidine (4i). White solid: 122 mg, 99% of yield;
mp 122−123 °C; 1H NMR (400 MHz, CDCl3) δ 7.80 (d, J = 8.2 Hz,
2H), 7.25−7.15 (m, 5H), 7.11−7.08 (m, 2H), 4.39 (s, 2H), 3.91 (p, J
= 6.6 Hz, 1H), 3.51−3.44 (m, 1H), 2.38 (s, 3H), 1.40 (d, J = 6.8 Hz,
6H), 0.91 (d, J = 6.6 Hz, 6H); 13C NMR (101 MHz, CDCl3) δ 162.6,
141.8, 141.2, 136.9, 134.5, 130.1, 129.1, 128.0, 127.0, 126.2, 126.1,
50.5, 48.2, 37.9, 21.5, 19.9, 19.8; IR (neat) ν 1541, 1451, 1373, 1260,
1136, 1083, 1050, 900, 808, 785, 715, 659 cm−1; EMM (ESI, TOF)
calc. for C21H28ClN2O2S [M + H]+ 407.1555, found 407.1547.
N1,N1-Diisopropyl-N2-(4-methylbenzenesulfonyl)-2-(2-
methoxyphenyl)acetamidine (4j). White solid: 109 mg, 90% of
N1,N1-Diethyl-N2-(4-methylbenzenesulfonyl)-2-phenylaceta-
midine (6a).21 White solid: 98 mg, 95% of yield; mp 116−117 °C;
1H NMR (400 MHz, CDCl3) δ 7.77 (d, J = 8.2 Hz, 2H), 7.28−7.15
(m, 5H), 7.11 (dd, J = 7.1, 1.8 Hz, 2H), 4.38 (s, 2H), 3.50 (q, J = 7.1
Hz, 2H), 3.20 (q, J = 7.1 Hz, 2H), 2.36 (s, 3H), 1.15 (t, J = 7.1 Hz,
3H), 0.94 (t, J = 7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 164.5,
141.7, 141.3, 134.4, 129.0, 128.8, 127.8, 126.7, 126.2, 43.4, 43.3, 36.6,
21.4, 13.4, 11.9; IR (neat) ν 1549, 1471, 1274, 1140, 1076, 827, 762,
724, 658 cm−1; EMM (ESI, TOF) calc. for C19H25N2O2S [M + H]+
345.1632, found 345.1636.
1
yield; mp 178−179 °C; H NMR (400 MHz, CDCl3) δ 7.81 (d, J =
8.2 Hz, 2H), 7.22−7.15 (m, 3H), 7.08 (dd, J = 7.4, 1.2 Hz, 1H), 6.86−
6.82 (m, 2H), 4.32 (s, 2H), 3.89−3.77 (m, 4H), 3.49−3.43 (m, 1H),
2.37 (s, 3H), 1.41 (d, J = 6.8 Hz, 6H), 0.88 (d, J = 6.6 Hz, 6H); 13C
NMR (101 MHz, CDCl3) δ 164.7, 156.0, 141.6, 141.4, 129.0, 128.5,
128.0, 126.2, 123.3, 120.9, 110.3, 55.5, 50.2, 47.9, 31.9, 21.4, 19.9; IR
(neat) ν 1544, 1493, 1444, 1373, 1261, 1245, 1130, 1107, 1077, 1052,
959, 816, 743, 688, 657 cm−1; EMM (ESI, TOF) calc. for
C22H31N2O3S [M + H]+ 403.2050, found 403.2050.
N1,N1-Dipropyl-N2-(4-methylbenzenesulfonyl)-2-phenylace-
tamidine (6b). Yellow solid: 95 mg, 85% of yield; mp 84−85 °C; 1H
NMR (400 MHz, CDCl3) δ 7.77 (d, J = 8.0 Hz, 2H), 7.29−7.10 (m,
7H), 4.38 (s, 2H), 3.48−3.28 (m, 2H), 3.17−2.99 (m, 2H), 2.36 (s,
3H), 1.60 (q, J = 7.6 Hz, 2H), 1.42−1.25 (m, 2H), 0.84 (td, J = 7.5, 1.1
Hz, 3H), 0.74 (td, J = 7.5, 1.8 Hz, 3H); 13C NMR (101 MHz, CDCl3)
δ 164.8, 141.6, 141.4, 134.5, 129.0, 128.8, 128.0, 126.8, 126.2, 50.8,
50.6, 36.8, 21.7, 21.4, 20.1, 11.5, 11.1; IR (neat) ν 1545, 1473, 1272,
1141, 1087, 953, 839, 726, 690 cm−1; EMM (ESI, TOF) calc. for
C21H29N2O2S [M + H]+ 373.1945, found 373.1947.
N1,N1-Diisopropyl-N2-(4-methylbenzenesulfonyl)-2-(2-
bromophenyl)acetamidine (4k). White solid: 112 mg, 83% of
1
yield; mp 191−192 °C; H NMR (400 MHz, CDCl3) δ 7.82 (d, J =
8.2 Hz, 2H), 7.56 (d, J = 7.5 Hz, 1H), 7.25−7.19 (m, 4H), 7.13−7.06
(m, 1H), 4.47 (s, 2H), 3.72 (p, J = 6.6 Hz, 1H), 3.55−3.40 (m, 1H),
2.38 (s, 3H), 1.41 (d, J = 6.8 Hz, 6H), 0.91 (d, J = 6.6 Hz, 5H); 13C
NMR (101 MHz, CDCl3) δ 163.2, 141.7, 141.3, 134.5, 132.8, 129.2,
129.1, 128.5, 127.9, 126.2, 123.9, 50.6, 48.1, 38.5, 21.5, 19.8, 19.8; IR
(neat) ν 1546, 1438, 1372, 1267, 1208, 1132, 1078, 1053, 1025, 955,
813, 754, 704, 669 cm−1; EMM (ESI, TOF) calc. for C21H28BrN2O2S
[M + H]+ 451.1050, found 451.1041.
N1,N1-Dibutyl-N2-(4-methylbenzenesulfonyl)-2-phenylaceta-
1
midine (6c). Yellow solid: 96 mg, 80% of yield; mp 66−67 °C; H
NMR (400 MHz, CDCl3) δ 7.78 (d, J = 8.2 Hz, 2H), 7.31−7.09 (m,
7H), 4.39 (s, 2H), 3.51−3.31 (m, 2H), 3.21−3.01 (m, 2H), 2.37 (s,
3H), 1.61−1.45 (m, 2H), 1.36−1.19 (m, 4H), 1.19−1.10 (m, 2H),
0.86 (t, J = 7.3 Hz, 3H), 0.81 (t, J = 7.3 Hz, 2H); 13C NMR (101
MHz, CDCl3) δ 164.6, 141.6, 141.5, 134.6, 128.9, 128.9, 128.9, 128.0,
126.8, 126.2, 49.0, 48.8, 36.9, 30.5, 28.7, 21.4, 20.2, 20.0, 13.8, 13.7; IR
(neat) ν 1552, 1474, 1258, 1135, 1084, 952, 858, 815, 728, 691, 675
cm−1; EMM (ESI, TOF) calc. for C23H33N2O2S [M + H]+ 401.2258,
found 401.2271.
N1,N1-Diisopropyl-N2-(4-methylbenzenesulfonyl)-2-(6-me-
thoxynaphtalen-2-yl)acetamidine (4l). White solid: 121 mg, 89%
of yield; mp 160−161 °C; 1H NMR (400 MHz, CDCl3) δ 77.82 (d, J
= 8.0 Hz, 2H), 7.66 (d, J = 8.4 Hz, 1H), 7.58 (d, J = 8.8 Hz, 1H), 7.39
(d, J = 2.0 Hz, 1H), 7.29 (dd, J = 8.4, 1.8 Hz, 1H), 7.20−7.06 (m, 4H),
4.51 (s, 2H), 4.07 (p, J = 6.6 Hz, 1H), 3.89 (s, 3H), 3.50−3.43 (m,
1H), 2.30 (s, 3H), 1.44 (d, J = 6.8 Hz, 6H), 0.84 (d, J = 6.5 Hz, 6H);
13C NMR (101 MHz, CDCl3) δ 163.7, 157.8, 141.6, 141.5, 133.3,
N1,N1-Dibenzyl-N2-(4-methylbenzenesulfonyl)-2-phenylace-
tamidine (6d). Clear oil: 104 mg, 74% of yield; 1H NMR (400 MHz,
CDCl3) δ 7.76 (d, J = 8.3 Hz, 2H), 7.37−7.11 (m, 15H), 7.05−6.91
(m, 2H), 4.71 (s, 2H), 4.49 (s, 2H), 4.37 (s, 2H), 2.38 (s, 3H); 13C
NMR (101 MHz, CDCl3) δ 166.4, 142.0, 140.9, 136.0, 134.9, 134.1,
129.2, 129.1, 129.0, 128.7, 128.3, 128.1, 128.1, 127.8, 127.0, 126.4,
51.2, 51.0, 37.0, 21.5; IR (neat) ν 1537, 1453, 1277, 1141, 1088, 853,
729, 691 cm−1; EMM (ESI, TOF) calc. for C29H29N2O2S [M + H]+
469.1945, found 469.1945.
129.9, 129.1, 129.0, 128.9, 127.4, 126.7, 126.3, 126.2, 119.0, 105.6,
55.3, 50.5, 48.1, 38.3, 21.4, 19.9; IR (neat) ν 1538, 1444, 1374, 1262,
1228, 1132, 1047, 843, 791, 730, 674 cm−1; EMM (ESI, TOF) calc. for
C26H33N2O3S [M + H]+ 453.2207, found 453.2216.
N1,N1-Diisopropyl-N2-(4-methylbenzenesulfonyl)-2-(thio-
phen-2-yl)phenylacetamidine (4m). White solid: 96 mg, 85% of
N1-Butyl-N1-ethyl-N2-(4-methylbenzenesulfonyl)-2-phenyla-
cetamidine (6e). Yellow solid: 91 mg, 81% of yield; mp 64−65 °C;
1
yield; mp 136−137 °C; H NMR (400 MHz, CDCl3) δ 7.81 (d, J =
E
J. Org. Chem. XXXX, XXX, XXX−XXX