4.1.8 ethyl 2,2-difluoro-2-((4-nitrobenzyl)thio)acetate (3h)
103.3 mg, yield: 82%, colorless oil; 1H NMR (400 MHz, CDCl3):
δ 7.29 (dd, J1 = 4.8 Hz, J2 = 3.2 Hz, 1H), 7.21 (s, 1H), 7.06 (d, J
= 6.0 Hz, 1H), 4.31 (q, J = 7.2 Hz, 2H), 4.15 (s, 2H), 1.34 (t, J =
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 161.6 (t, J = 32.6
Hz), 135.6, 127.9, 126.3, 123.6, 120.1 (t, J = 285.0 Hz), 63.7,
27.5 (t, J = 3.9 Hz), 13.7; 19F NMR (376 MHz, CDCl3): δ -83.2.
IR (neat): υ 2985, 1766, 1470, 1412, 1371, 1301, 1103, 1014,
787, 720, 617 cm-1. MS (EI): m/z (%) = 252 (11) [M]+·, 85 (4), 97
(100), 129 (30). HRMS (EI) calcd. for C9H10F2O2S2 [M]+·:
252.0090; found 252.0089.
ACCEPTED MANUSCRIPT
87.3 mg, yield: 60%, pale yellow oil; 1H NMR (400 MHz,
CDCl3): δ 8.17 (d, J = 8.8 Hz, 2H), 7.52 (d, J = 8.8 Hz, 2H), 4.32
(q, J = 6.8 Hz, 2H), 4.16 (s, 2H), 1.33 (t, J = 7.2 Hz, 3H); 13C
NMR (100 MHz, CDCl3): δ 161.2 (t, J = 31.8 Hz), 147.3, 143.6,
129.8, 123.9, 120.1 (t, J = 286.2 Hz), 63.9, 32.3 (t, J = 3.8 Hz),
13.8; 19F NMR (376 MHz, CDCl3): δ -82.43. IR (neat): υ 2987,
1766, 1522, 1371, 1348, 1304, 1108, 1013, 987, 858, 708 cm-1.
MS (EI): m/z (%) = 291 (3) [M]+·, 89 (20), 106 (15), 136 (25),
168 (100). HRMS (EI): calcd. for C11H11F2NO4S [M]+· 291.0377;
found 291.0370.
4.1.14 ethyl 2,2-difluoro-2-(prop-2-yn-1-ylthio)acetate (3n)
1
4.1.9
ethyl
2,2-difluoro-2-((4-(trifluoromethyl)benzyl)thio)-
67.9 mg, yield: 70%, colorless oil; H NMR (400 MHz, CDCl3):
acetate (3i)
δ 4.35 (q, J = 7.2 Hz, 2H), 3.62 (d, J = 2.4 Hz, 2H), 2.27 (t, J =
2.4 Hz, 1H), 1.36 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 161.2 (t, J = 32.4 Hz), 119.9 (t, J = 285.9 Hz), 77.7,
72.3, 63.9, 17.0 (t, J = 4.8 Hz), 13.8; 19F NMR (376 MHz,
CDCl3): δ -83.9. IR (neat): υ 3302, 2987, 1769, 1304, 1245,
1105, 989, 721, 652 cm-1. MS (EI): m/z (%) = 194 (1) [M]+·, 45
(47), 71 (100), 77 (60), 121 (55), 166 (98). HRMS (EI) calcd. for
C7H8F2O2S [M]+·: 194.0213; found 194.0220.
111.5 mg, yield: 71%, colorless oil; 1H NMR (400 MHz, CDCl3):
δ 7.58 (d, J = 8.4 Hz, 2H), 7.47 (d, J = 8.0 Hz, 2H), 4.31 (q, J =
7.2 Hz, 2H), 4.14 (s, 2H), 1.33 (t, J = 7.2 Hz, 3H). 13C NMR (100
MHz, CDCl3): δ 161.4 (t, J = 32.6 Hz), 140.0, 130.0 (q, J = 32.6
Hz), 129.3, 125.6 (q, J = 3.8 Hz), 123.9 (q, J = 271.0 Hz), 120.1
(t, J = 285.5 Hz), 63.7, 32.4 (t, J = 3.0 Hz), 13.7. 19F NMR (376
MHz, CDCl3): δ -62.72 (s, 3F), -82.77 (s, 2F). IR (neat): υ 2989,
1768, 1618, 1372, 1325, 1126, 1067, 1018, 988, 849, 724 cm-1.
MS (EI): m/z (%) = 314 (1) [M]+·, 96 (10), 109 (16), 159 (100),
191 (99). HRMS (EI) calcd. for C12H11F5O2S [M]+·: 314.0400;
found 314.0394.
4.1.15 ethyl 2,2-difluoro-2-(phenethylthio)acetate (3o)
114.4 mg, yield: 88%, colorless oil; 1H NMR (400 MHz, CDCl3):
δ 7.29 (t, J = 7.2 Hz, 2H), 7.24-7.18 (m, 3H), 4.33 (q, J = 6.8 Hz,
2H), 3.11 (t, J = 6.8 Hz, 2H), 2.96 (t, J = 6.8 Hz, 2H), 1.33 (t, J =
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 161.7 (t, J = 32.5
Hz), 139.2, 128.6, 128.5, 126.7, 120.7 (t, J = 285.7 Hz), 63.6,
36.2, 30.0 (t, J = 3.1 Hz), 13.8; 19F NMR (376 MHz, CDCl3): δ -
82.5. IR (neat): υ 2985, 1767, 1497, 1454, 1371, 1300, 1101,
1015, 748, 717, 698 cm-1. MS (EI): m/z (%) = 260 (1) [M]+·, 77
(12), 91 (64), 104 (100). HRMS (EI) calcd. for C12H14F2O2S
[M]+·: 260.0683; found 260.0674.
4.1.10 ethyl 2,2-difluoro-2-((2-nitrobenzyl)thio)acetate (3j)
71.3 mg, yield: 49%, colorless oil; H NMR (400 MHz, CDCl3):
1
δ 8.07 (dd, J1 = 8.4 Hz, J2 = 1.2 Hz, 1H), 7.62-7.53 (m, 2H),
7.49-7.44 (m, 1H), 4.40 (s, 2H), 4.31 (q, J = 7.2 Hz, 2H), 1.32 (t,
J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 161.4 (t, J =
32.6 Hz), 147.8, 133.8, 133.0, 132.4, 129.0, 125.5, 120.4 (t, J =
285.4 Hz), 63.8, 30.8 (t, J = 3.8 Hz), 13.7; 19F NMR (376 MHz,
CDCl3): δ -82.54. IR (neat): υ 2987, 1766, 1526, 1344, 1304,
1106, 987, 808, 707 cm-1. MS (EI): m/z (%) = 291 (1) [M]+·, 65
(78), 78 (100), 97 (79), 136 (83). HRMS (EI) calcd. for
C11H11F2NO4S [M]+·: 291.0377; found 291.0375.
4.1.16 ethyl 2,2-difluoro-2-((4-fluorophenethyl)thio)acetate(3p)
112.6 mg, yield: 81%, colorless oil; 1H NMR (400 MHz, CDCl3):
δ 7.18-7.15 (m, 2H), 7.01-6.91 (m, 2H), 4.35 (q, J = 6.8 Hz, 2H),
3.10 (t, J = 7.2 Hz, 2H), 2.95 (t, J = 7.2 Hz, 2H), 1.36 (t, J = 7.2
Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 161.7 (d, J = 244.0 Hz),
161.6 (t, J = 32.5 Hz), 134.8 (d, J = 3.9 Hz), 130.0 (d, J = 7.8
Hz), 120.6 (t, J = 284.3 Hz), 115.3 (d, J = 21.7Hz), 63.6, 35.3,
30.1 (t, J = 3.1 Hz), 13.7; 19F NMR (376 MHz, CDCl3): δ -82.5,
116.1. IR (neat): υ 2986, 1766, 1510, 1447, 1371, 1301, 1224,
1102, 1015, 825, 726, 532 cm-1. MS (EI): m/z (%) = 278 (1)
[M]+·, 96 (5), 109 (84), 122 (100). HRMS (EI) calcd. for
C12H13F3O2S [M]+·: 278.0588; found 278.0581.
4.1.11 ethyl 2,2-difluoro-2-((3-nitrobenzyl)thio)acetate (3k)
87.3 mg, yield: 60%, colorless oil; H NMR (400 MHz, CDCl3):
1
δ 8.21 (s, 1H), 8.12 (d, J = 8.4 Hz, 1H), 7.69 (d, J = 8.0 Hz, 1H),
7.51 (t, J = 8.0 Hz, 1H), 4.32 (q, J = 7.6 Hz, 2H), 4.18 (s, 2H),
1.33 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 161.3 (t,
J = 32.6 Hz), 148.3, 138.3, 135.0, 129.7, 123.8, 122.7, 120.1 (t, J
= 285.5 Hz), 63.9, 32.3 (t, J = 3.8 Hz), 13.7; 19F NMR (376 MHz,
CDCl3): δ -82.50 (s, 2F). IR (neat): υ 2987, 1765, 1530, 1352,
1305, 1250, 1100, 987, 810, 720 cm-1. MS (EI): m/z (%) = 291
(1) [M]+·, 90 (47), 109 (16), 136 (71), 168 (100). HRMS (EI)
calcd. for C11H11F2NO4S [M]+·: 291.0377; found 291.0376.
4.1.17 ethyl 2-((chloromethyl)thio)-2,2-difluoroacetate (3q)
1
86.7 mg, yield: 85%, colorless oil; H NMR (400 MHz, CDCl3):
δ 4.92 (s, 2H), 4.40 (q, J = 7.2 Hz, 2H), 1.39 (t, J = 7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3): δ 161.1 (t, J = 32.6 Hz), 119.1 (t, J
= 287.8 Hz), 64.2, 42.5 (t, J = 4.4 Hz), 13.7; 19F NMR (376 MHz,
CDCl3): δ -84.7. IR (neat): υ 2988, 1769, 1372, 1305, 1239,
1127, 1014, 986, 854, 731 cm-1. MS (EI): m/z (%) = 204 (11)
[M]+·, 73 (1), 77 (54), 131 (35), 91 (100), 162 (99), 203 (95).
HRMS (EI) calcd. for C5H7ClF2O2S [M]+·: 203.9823; found
203.9831.
4.1.12 ethyl 2-(cinnamylthio)-2,2-difluoroacetate (3l)
125.2 mg, yield: 92%, colorless oil; 1H NMR (400 MHz, CDCl3):
δ 7.35-7.21 (m, 5H), 6.56 (d, J = 15.6 Hz, 1H), 6.20 (dt, J1 =
14.8 Hz, J2 = 7.6 Hz, 1H), 4.30 (q, J = 6.8 Hz, 2H), 3.69 (d, J =
7.2 Hz, 2H) 4.11 (s, 2H), 1.32 (t, J = 7.2 Hz, 3H); 13C NMR (100
MHz, CDCl3): δ 161.6 (t, J = 33.1 Hz), 136.1, 133.9, 128.5,
127.9, 126.3, 123.4, 120.4 (t, J = 284.4 Hz), 63.5, 31.4 (t, J = 3.1
Hz), 13.7; 19F NMR (376 MHz, CDCl3): δ -82.66. IR (neat): υ
2985, 1766, 1496, 1448, 1371, 1301, 1232, 1104, 1024, 961, 834,
750, 696 cm-1. MS (EI): m/z (%) = 272 (3) [M]+·, 77 (3), 91 (12),
115 (50), 117 (100), 149 (28). HRMS (EI) calcd. for C13H14F2O2S
[M]+·: 272.0683; found 272.0682.
4.1.18 ethyl 2,2-difluoro-2-(hexylthio)acetate (3r)
1
93.6 mg, yield: 78%, colorless oil; H NMR (400 MHz, CDCl3):
δ 4.33 (d, J = 7.2 Hz, 2H), 2.84 (t, J = 7.2 Hz, 2H), 1.68-1.61 (m,
2H), 1.41-1.33 (m, 5H), 1.28-1.26 (m, 4H); 13C NMR (100 MHz,
CDCl3): δ 161.8 (t, J = 33.2 Hz), 120.6 (t, J = 283.3 Hz), 63.4,
31.1, 29.4, 28.6 (t, J = 2.9 Hz), 28.2, 22.3, 13.8, 13.7; 19F NMR
(376 MHz, CDCl3): δ -83.0. IR (neat): υ 2959, 1769, 1467, 1371,
1290, 1101, 1017, 986, 835, 723 cm-1. MS (EI): m/z (%) = 240
4.1.13 ethyl 2,2-difluoro-2-((thiophen-3-ylmethyl)thio)acetate
(3m)