80
P. Cherkupally, P. Beier / Journal of Fluorine Chemistry 141 (2012) 76–82
1
1
(m, 2H), 7.58 (d, 3JHH = 8.5 Hz, 1H), 7.78–7.84 (m, 3H), 7.96 (s, 1H);
(ddd, JCF = 267.6, 266.0 Hz, JCP = 209.4 Hz), 123.0–123.1 (m),
3
13C NMR (100 MHz, CDCl3):
d
16.1 (d, JCP = 5.6 Hz), 16.2 (d,
126.6, 127.9, 128.5, 135.5, 136.2; 19F NMR (376 MHz, CDCl3):
d
3JCP = 5.6 Hz), 61.0 (ddd, 2JCF = 24.8, 21.1 Hz, 2JCP = 14.7 Hz), 64.7 (d,
2JCP = 6.3 Hz), 64.8 (d, 2JCP = 6.2 Hz), 113.9, 118.5 (ddd, 1JCF = 268.6,
266.6 Hz, 1JCP = 209.2 Hz), 118.6, 126.0, 126.1, 126.3, 127.6, 128.0,
À112.4 (ddd, JFF = 301.0 Hz, JFP = 102.8 Hz, JFH = 9.9 Hz, 1F),
2
2
3
2 2 3
À120.6 (ddd, JFF = 301.0 Hz, JFP = 103.9 Hz, JFH = 18.1 Hz, 1F);
31P NMR (162 MHz, CDCl3): 7.44 (dd, 2JPF = 103.9, 102.8 Hz); FTIR
(film):
max (cm–1) 3316, 3083, 3060, 3027, 2982, 2959, 2931, 2872,
d
128.1, 128.4, 129.2, 131.9 (d, 3JCF = 5.1 Hz), 133.1, 133.4, 145.7; 19
F
v
NMR (376 MHz, CDCl3):
d
À110.8 (ddd, 2JFF = 304.5 Hz,
1651, 1599, 1578, 1496, 1270, 1165, 1030; MS (EI): m/z (rel. int.)
189 (15), 188 (100), 165 (2), 132 (4), 115 (8); HRMS (ESI): m/z calcd
for C18H29F2NO3P [MH]+ 376.18476, found 376.18481.
3
2
2JFP = 101.7 Hz, JFH = 8.2 Hz, 1F), À120.6 (ddd, JFF = 304.5 Hz,
3
2JFP = 104.4 Hz, JFH = 20.2 Hz, 1F); 31P NMR (162 MHz, CDCl3):
d
2
6.80 (dd, JPF = 104.4, 101.7 Hz); FTIR (film): vmax (cm–1) 3311,
3117, 3057, 3015, 1603, 1524, 1501, 1258, 1176, 1030, 1020; MS
(EI): m/z (rel. int.) 419 (6) [M]+, 233 (20), 232 (100), 190 (5), 104
(11), 77 (8); HRMS (ESI): m/z calcd for C22H25F2NO3P [MH]+
420.15346, found 420.15339.
4.3.15. Diethyl 1,1-difluoro-2-benzylamino-3-
methylbutylphosphonate (3o)
Colourless oil (161 mg, 68%). Rf = 0.29 (EtOAc–hexane, 20:80);
1H NMR (500 MHz, CDCl3):
d
0.97 (d, JHH = 6.8 Hz, 3H), 1.05 (d,
3
3JHH = 6.9 Hz, 3H), 1.33 (dt, JHH = 7.1 Hz, JHP = 0.6 Hz, 3H), 1.37
3
4
3
4
4.3.12. Diethyl 2-(2-naphthyl)-1,1-difluoro-2-
butylaminoethylphosphonate (3l)
(dt, JHH = 7.1 Hz, JHP = 0.6 Hz, 3H), 1.50 (br s, 1H), 2.21–2.30 (m,
2
1H), 3.04–3.12 (m, 1H), 3.90 (d, JHH = 12.7 Hz, 1H), 4.08 (d,
Colourless oil (202 mg, 78%). Rf = 0.22 (EtOAc–hexane, 20:80); 1H
2JHH = 12.7 Hz, 1H), 4.18–4.32 (m, 4H), 7.22–7.26 (m, 1H), 7.29–
NMR (400 MHz, CDCl3):
d
0.84 (t, 3JHH = 7.3 Hz, 3H), 1.21–1.36 (m,
7.33 (m, 2H), 7.38–7.40 (m, 2H); 13C NMR (125.7 MHz, CDCl3):
d
3
3
3
8H), 1.38–1.53 (m, 2H), 1.92 (br s, 1H), 2.52 (t, JHH = 7.2 Hz, 2H),
4.03–4.36 (m, 4H), 4.42 (ddd, 3JHF = 21.5, 8.6 Hz, 3JHP = 2.9 Hz, 1H),
16.3 (d, JCP = 5.1 Hz), 16.4 (d, JCP = 5.0 Hz), 17.0, 21.4, 28.0, 54.1,
63.9 (ddd, 2JCF = 20.2, 18.6 Hz, 2JCP = 14.7 Hz), 64.1 (d, 2JCP = 6.7 Hz),
7.45–7.54 (m, 3H), 7.82–7.87 (m, 4H); 13C NMR (100 MHz, CDCl3):
d
64.2 (d, JCP = 6.9 Hz), 122.6 (dt, JCF = 267.1 Hz, JCP = 206.7 Hz),
127.0, 128.2, 128.3, 140.5; 19F NMR (470.4 MHz, CDCl3):
À112.3
2
1
1
3
3
13.8, 16.2 (d, JCP = 5.7 Hz), 16.3 (d, JCP = 5.8 Hz), 20.2, 32.0, 47.2,
d
2
2
2
2
2
3
64.1 (d, JCP = 6.9 Hz), 64.5 (d, JCP = 6.5 Hz), 64.8 (ddd, JCF = 23.4,
19.2 Hz, 2JCP = 15.4 Hz), 119.5 (ddd, 1JCF = 269.1, 265.5 Hz,
(ddd, JFF = 301.9 Hz, JFP = 107.7 Hz, JFH = 13.7 Hz, 1F), À114.9
2 2 3
(ddd, JFF = 301.9 Hz, JFP = 106.9 Hz, JFH = 19.4 Hz, 1F); 31P NMR
2
1JCP = 210.1 Hz), 126.0, 126.1, 126.2, 127.6, 127.9, 128.9, 132.6
(162 MHz, CDCl3):
v
max (cm–1) 3350, 3087, 3064, 3029, 2988, 2966, 2934, 2914, 2876,
1605, 1585, 1496, 1269, 1164, 1030; MS (EI): m/z (rel. int.) 306
(12), 162 (51), 106 (49), 91 (100), 65 (6); HRMS (ESI): m/z calcd for
C
16H27F2NO3P [MH]+ 350.16911, found 350.16837.
d
7.83 (dd, JPF = 107.7, 106.9 Hz); FTIR (film):
3
(dd, JCF = 6.1, 1.4 Hz), 133.0, 133.3; 19F NMR (376 MHz, CDCl3):
d
2
2
3
À111.4 (ddd, JFF = 302.1 Hz, JFP = 102.3 Hz, JFH = 8.6 Hz, 1F),
2
2
3
À122.0 (ddd, JFF = 302.1 Hz, JFP = 104.9 Hz, JFH = 21.5 Hz, 1F);
31P NMR (162 MHz, CDCl3): 7.50 (dd, 2JPF = 104.9, 102.3 Hz); FTIR
(film):
max (cm–1) 3317, 3057, 2959, 2930, 2872, 1601, 1509, 1268,
d
v
1165, 1031; MS (EI): m/z (rel. int.) 308 (2), 213 (17), 212 (100), 190
(8), 156(4), 129 (6), 109 (3); HRMS(ESI): m/z calcd forC20H29F2NO3P
[MH]+ 400.18476, found 400.18478.
4.3.16. t-Butyl [2-(diethoxyphosphoryl)-2,2-difluoro-1-phenylethyl]
carbamate (3p)
Colourless oil (247 mg, 88%). Rf = 0.13 (EtOAc–hexane, 20:80);
3
1H NMR (400 MHz, CDCl3):
d
1.13 (t, JHH = 6.6 Hz, 3H), 1.31 (t,
4.3.13. (E)-Diethyl 1,1-difluoro-4-phenyl-2-phenylamino-3-
butenylphosphonate (3m)
3JHH = 6.9 Hz, 3H), 1.43 (s, 9H), 3.90–4.25 (m, 4H), 5.28–5.40 (m,
1H), 5.91 (d, JHH = 8.9 Hz, 1H), 7.33–7.42 (m, 5H); 13C NMR
(100 MHz, CDCl3): d 15.9 (d, JCP = 5.8 Hz), 16.2 (d, JCP = 5.6 Hz),
3
3
3
Light yellow solid (249 mg, 86%). Rf = 0.24 (EtOAc–hexane,
20:80); mp 110–111 8C; 1H NMR (400 MHz, CDCl3):
d
1.29 (dt,
28.2, 56.7–57.5 (m), 64.4 (d, JCP = 7.0 Hz), 64.7 (d, JCP = 6.8 Hz),
80.1, 118.3 (dt, 1JCF = 266.5 Hz, 1JCP = 207.7 Hz), 128.2, 128.4, 128.5,
2
2
3JHH = 7.1 Hz, 4JHP = 0.5 Hz, 3H), 1.31 (dt, 3JHH = 7.1 Hz,
3
4JHP = 0.5 Hz, 3H), 4.09–4.31 (m, 4H), 4.38 (d, JHH = 9.3 Hz, 1H),
134.2, 154.7; 19F NMR (376 MHz, CDCl3):
d
À112.8 (ddd,
4.63–4.75 (m, 1H), 6.24 (dd, 3JHH = 15.9, 6.3 Hz, 1H), 6.72–6.78 (m,
2JFF = 303.7 Hz, JFP = 103.3 Hz, JFH = 10.9 Hz, 1F), À116.5 (ddd,
2
3
4H), 7.16–7.31 (m, 5H), 7.35–7.38 (m, 2H); 13C NMR (100 MHz,
2JFF = 303.7 Hz, JFP = 102.7 Hz, JFH = 17.3 Hz, 1F); 31P NMR
2
3
3
2
2
CDCl3):
d
16.3 (d, JCP = 5.7 Hz), 59.3 (ddd, JCF = 24.2, 22.4 Hz,
(162 MHz, CDCl3):
d
5.53 (dd, JPF = 103.3, 102.7 Hz); FTIR (film):
max (cm–1) 3301, 3066, 3035, 2981, 2933, 2872, 1720, 1270, 1167,
2JCP = 15.2 Hz), 64.6 (d, JCP = 6.7 Hz), 64.7 (d, JCP = 7.0 Hz), 113.9,
v
2
2
1
1
118.7, 119.1 (ddd, JCF = 268.4, 267.4 Hz, JCP = 208.5 Hz), 121.9–
1021; MS (EI): m/z (rel. int.) 320 (4), 206 (19), 150 (56), 132 (29),
106 (100), 57 (28); HRMS (ESI): m/z calcd for C17H26F2NNaO5P
[MNa]+ 416.14089, found 416.14053.
122.0 (m), 126.7, 128.1, 128.5, 129.3, 134.8, 136.1, 146.1; 19F NMR
2
2
(376 MHz, CDCl3):
d
À112.8 (ddd, JFF = 301.7 Hz, JFP = 103.4 Hz,
3JFH = 9.6 Hz, 1F), À119.1 (ddd, JFF = 301.7 Hz, JFP = 101.7 Hz,
2 2
3JFH = 17.4 Hz, 1F); 31P NMR (162 MHz, CDCl3):
d
6.77 (dd,
4.3.17. Diethyl 1,1,3,3,3-pentafluoro-2-phenyl-2-
phenylaminopropylphosphonate (3s)
2JPF = 103.4, 101.7 Hz); FTIR (film): vmax (cm–1) 3302, 3119,
3057, 3031, 3005, 1600, 1578, 1533, 1498, 1255, 1189, 1051,
1035; MS (EI): m/z (rel. int.) 395 (4) [M]+, 209 (17), 208 (100), 130
(8), 115 (11), 91 (9), 77 (10); HRMS (ESI): m/z calcd for
Colourless oil (244 mg, 95%). Rf = 0.44 (EtOAc–hexane, 20:80);
3
4
1H NMR (400 MHz, CDCl3):
d 1.32 (dt, JHH = 7.1 Hz, JHP = 0.8 Hz,
3
4
3H), 1.42 (dt, JHH = 7.1 Hz, JHP = 0.7 Hz, 3H), 4.21–4.39 (m, 4H),
6.15 (br s, 1H), 6.45 (d, 3JHH = 8.3 Hz, 2H), 6.71–6.75 (m), 6.98–7.04
C
20H26F2NO3P [MH]+ 396.15346, found 396.15368.
(m, 2H), 7.39–7.48 (m, 3H), 7.73 (d, JHH = 7.4 Hz, 2H); 13C NMR
3
4.3.14. (E)-Diethyl 1,1-difluoro-4-phenyl-2-butylamino-3-
(125.7 MHz, CDCl3):
d
16.1 (d, 3JCP = 5.9 Hz), 16.2 (d, 3JCP = 5.6 Hz),
2
2
butenylphosphonate (3n)
65.7 (d, JCP = 7.9 Hz), 66.0 (d, JCP = 7.1 Hz), 71.9–72.3 (m), 116.0
(ddd, 1JCF = 275.8, 273.1 Hz, 1JCP = 202.8 Hz), 117.1, 119.4, 124.9 (q,
1JCF = 293.9 Hz), 128.0, 128.3, 128.4–128.5 (m), 129.5, 130.1, 143.2;
Pale yellow oil (183 mg, 84%). Rf = 0.16 (EtOAc–hexane, 20:80);
3
1H NMR (400 MHz, CDCl3):
d
0.90 (t, JHH = 7.3 Hz, 3H), 1.29–1.56
4
(m, 11H), 1.41–1.56 (m, 2H), 2.54–2.61 (m, 1H), 2.71–2.77 (m, 1H),
3.72–3.83 (m, 1H), 4.18–4.34 (m, 4H), 6.10 (dd, 3JHH = 15.9, 8.6 Hz),
19F NMR (376 MHz, CDCl3):
d
À62.0 (dd, JFF = 11.3, 10.2 Hz, 3F),
À112.7 to À113.1 (m, 2F); 31P NMR (162 MHz, CDCl3):
d 4.25 (dd,
6.64 (d, 3JHH = 15.9 Hz), 7.23–7.35 (m, 3H), 7.40–7.43 (m, 2H); 13
C
2JPF = 102.7, 98.8 Hz); FTIR (film): vnmax (cm–1) 3337, 3061, 3015,
1603, 1552, 1500, 1267, 1167, 1026; MS (EI): m/z (rel. int.) 437 (8)
[M]+, 251 (16), 250 (100), 180 (11), 77 (12); HRMS (ESI): m/z calcd
for C19H21F5NNaO3P [MNa]+ 460.10714, found 460.10698.
3
NMR (100 MHz, CDCl3):
d
13.9, 16.2 (d, JCP = 5.7 Hz), 16.3 (d,
2
3JCP = 5.8 Hz), 20.3, 32.1, 47.0, 63.6 (ddd, JCF = 23.4, 20.5 Hz,
2
2
2JCP = 15.4 Hz), 64.1 (d, JCP = 6.8 Hz), 64.4 (d, JCP = 6.5 Hz), 119.8