G
Synthesis
S. N. Arbuzova et al.
Paper
1
3
3
3
3
2
2
C NMR (100.62 MHz, CDCl ): = 146.5 (d, JC,P = 14.2 Hz, C , Ph-N),
H, H , naphthyl), 6.55 (d, J = 7.6 Hz, 1 H, H , naphthyl), 5.82 (tt, J
3
i
H,H
H,F
4
3
2
3
1
1
35.1 (C , Ph-C), 130.4 (C , Ph-N), 130.1 (d, JC,P = 2.6 Hz, C , Ph-C),
29.9 (d, J = 3.3 Hz, C , Ph-C), 128.8 (d, J = 6.3 Hz, C , Ph-C), 120.5
= 52.7 Hz, J = 3.8 Hz, 1 H, HCF ), 5.62 (tt, J = 52.7 Hz, J = 3.8
Hz, 1 H, HCF ), 5.23 (br s, 1 H, NH), 5.16 (d, JH,P = 24.2 Hz, 1 H, CH),
4.60–4.48 (m, 1 H, H , C H ), 4.44–4.31 (m, 1 H, H , C H ), 4.39–4.26
(m, 1 H, H , C H ), 3.99–3.86 (m, 1 H, H , C H ).
i
m
m
H,F 2 H,F H,F
5
3
2
C,P
p
C,P
o
2
1
2
(
C , Ph-N), 115.3 (C , Ph-N), 114.7 (ttd, J = 250.4 Hz, J = 28.0 Hz,
p
o
C,F
C,F
a′
a
2
a′′
a
2
3
JC,P = 7.0 Hz, CF ), 114.5 (ttd, J = 250.7 Hz, J = 28.0 Hz, 3JC,P = 7.3
1
2
2
C,F
C,F
b′ b 2 b′′ b 2
1
2
1
Hz, CF ), 110.0 (tt, J = 250.2 Hz, J = 36.0 Hz, HCF ), 109.9 (tt, J
2
C H ), 63.2 (td, J = 30.7 Hz, J = 6.8 Hz, C H ), 57.2 (d, J = 155.3
Hz, CH).
=
13
3
1
2
C,F
C,F
2
C,F
C NMR (100.62 MHz, CDCl ): = 140.6 (d, J = 15.2 Hz, C , naphth-
3 C,P
2
2
2
50.2 Hz, JC,F = 35.8 Hz, HCF ), 63.5 (td, JC,F = 29.9 Hz,
J
= 6.8 Hz,
4a
2
2
2
C,P
1
yl), 134.4 (C , naphthyl), 133.9 (d, JC,P = 2.0 Hz, C , C H ), 129.3 (d,
i 6 5
2
a
2
C,F
C,P
b
2
C,P
4
JC,P = 2.8 Hz, C , C H ), 129.1 (d, 5J = 3.5 Hz, C , C H ), 128.9 (C ,
5
m 6 5 C,P p 6 5
3
7
naphthyl), 127.8 (d, J = 6.1 Hz, C , C H ), 126.3 (C , naphthyl), 126.1
(C , naphthyl), 125.7 (C , naphthyl), 124.4 (d, J = 0.7 Hz, C , naph-
C,P
o
6
5
19
3
6
4
8a
F NMR (376.50 MHz, CDCl ): = –137.10, –137.29, –137.92, –138.20
3
C,P
2
4
8
1
(m, J = 53.0 Hz, 4 F, HCF ), –124.34, –124.60, –124.90, –125.23 (m,
thyl), 120.0 (C , naphthyl), 119.9 (C , naphthyl), 113.8 (ttd, J = 250.5
C,F
F,H
2
Hz, J = 28.2 Hz, J = 7.0 Hz, CF ), 113.6 (ttd, J = 250.0 Hz, 2JC,F
2
3
1
=
4
F, CF2).
C,F
C,P
2
C,F
3
1
C,F = 250.4 Hz, 2
31
28.0 Hz,
J
C,P = 7.4 Hz, CF
2
), 109.2 (tt,
J
J
C,F = 36.3 Hz,
P NMR (161.98 MHz, CDCl ): = 25.9.
3
1
2
2
HCF ), 109.0 (tt, J = 250.3 Hz, J = 35.9 Hz, HCF ), 107.6 (C , naph-
2
C,F
C,F
2
Anal. Сalcd for C19H18F NO P (491.312): С, 46.45; Н, 3.69; N, 2.85.
Found: C, 46.83; Н, 3.41; N, 3.04.
2
2
2
8
3
thyl), 62.7 (td, J = 30.2 Hz, J = 6.5 Hz, C H ), 62.4 (td, J = 30.4
C,F
C,P
1
a
2
C,F
2
Hz, J = 6.5 Hz, C H ), 56.5 (d, J = 155.6 Hz, CH).
C,P
b
2
C,P
1
9
F NMR (376.50 MHz, CDCl ): = –136.91, –137.17, –137.66, –138.03
3
Bis(2,2,3,3-tetrafluoropropyl) {[(2-Methylphenyl)amino](phe-
nyl)methyl}phosphonate (3h)
2
(m, J = 52.7 Hz, 4 F, HCF ), –124.15, –124.47, –124.62, –125.07 (m,
F,H
2
4
F, CF2).
Purified by Method B; yellowish oil; yield: 475 mg (94%).
31
P NMR (161.98 MHz, CDCl ): = 25.8.
3
IR (film): 3326, 3333, 3063, 3024, 2969, 2924, 2900, 2863, 2741,
Anal. Сalcd for C23H20F NO P (541.371): С, 51.03; Н, 3.72; N, 2.59.
Found: C, 51.05; Н, 3.40; N, 2.24.
8
3
2
1
1
571, 2249, 1742, 1692, 1597, 1511, 1453, 1407, 1305, 1260, 1241,
208, 1110, 1059, 940, 874, 837, 750, 700, 676, 550, 467 cm–
1
.
H NMR (400.13 MHz, CDCl ): = 7.49–7.45 (m, 2 H, H , Ph-C), 7.42–
3
o
Bis(2,2,3,3-tetrafluoropropyl) {[(4-Ethoxyphenyl)amino](phe-
nyl)methyl}phosphonate (3j)
3
7.38 (m, 2 H, H , Ph-C), 7.37–7.33 (m, 1 H, H , Ph-C), 7.09 (d, J = 8.4
m p H,H
3
3
3
5
Hz, 1 H, H , Ar-N), 7.02 (dd, J = 8.4 Hz, J = 8.0 Hz, 1 H, H , Ar-N),
H,H
H,H
4
3
3
3
Purified by Method B; yield: 476 mg (89%); white solid; mp 66–68 °C.
6.72 (dd, J = 8.4 Hz, J = 7.4 Hz, 1 H, H , Ar-N), 6.52 (d, J = 8.0
H,H
H,H
H,H
6
2
3
Hz, 1 H, H , Ar-N), 5.77 (tt, J = 53.0 Hz, J = 4.0 Hz, 1 H, HCF ), 5.58
IR (KBr): 3342, 3113, 3066, 3041, 2988, 2964, 2936, 2892, 1515, 1482,
1452, 1396, 1353, 1241, 1115, 1054, 930, 862, 829, 788, 730, 705,
675, 588, 552, 464 cm .
H,F
H,F
2
2
3
2
(tt, J = 53.0 Hz, J = 4.0 Hz, 1 H, HCF ), 5.00 (d, J = 24.0 Hz, 1 H,
H,F H,F 2 H,P
–1
CH), 4.50 (br, 1 H, NH), 4.52–4.41 (m, 1 H, H , C H ), 4.37–4.24 (m, 1
a′
a
2
H, H , C H ), 4.33–4.21 (m, 1 H, H , C H ), 3.95–3.83 (m, 1 H, H ,
1
a′′
a
2
b′
b
2
b′′
H NMR (400.13 MHz, CDCl ): = 7.47–7.43 (m, 2 H, H , Ph-C), 7.40–
3 o
C H ), 2.27 (s, 3 H, CH ).
b
2
3
7.36 (m, 2 H, H , Ph-C), 7.36–7.33 (m, 1 H, H , Ph-C), 6.75–6.71 (m, 2
m
p
1
3
3
1
3,5
2,6
2
C NMR (100.62 MHz, CDCl ): = 143.5 (d, J = 14.0 Hz, C , Ar-N),
H, H , Ar-N), 6.64–6.59 (m, 2 H, H , Ar-N), 5.79 (tt, JH,F = 53.0 Hz,
3
C,P
2
3
4
3
JH,F = 4.0 Hz, 1 H, HCF ), 5.57 (tt, 2JH,F = 53.0 Hz, JH,F = 4.0 Hz, 1 H,
3
1
34.2 (d, JC,P = 1.6 Hz, C , Ph-C), 130.5 (C , Ar-N), 129.0 (d, JC,P = 2.7
i
2
5
3
2
3
Hz, C , Ph-C), 128.8 (d, J = 3.4 Hz, C , Ph-C), 127.7 (d, J = 6.1 Hz,
C , Ph-C), 127.0 (C , Ar-N), 123.6 (C , Ar-N), 119.2 (C , Ar-N), 113.7
HCF ), 4.87 (dd, J = 23.8 Hz, J = 8.8 Hz, 1 H, CH), 4.55–4.42 (m, 1
H, H , C H ), 4.44–4.38 (m, 1 H, NH), 4.39–4.30 (m, 1 H, H , C H ),
a′ a 2 a′′ a 2
4.31–4.20 (m, 1 H, H , C H ), 3.91 (q, J = 7.0 Hz, 2 H, MeCH ), 3.94–
3.82 (m, 1 H, H , C H ), 1.34 (t, J = 7.0 Hz, 3 H, CH3).
b′′ b 2 H,H
m
C,P
p
C,P
2 H,P H,H
5
2
4
o
1
2
3
1
3
(ttd, J = 250.5 Hz, J = 28.0 Hz, J = 7.2 Hz, CF ), 113.6 (ttd, J
=
C,F
C,F
C,P
2
C,F
b′ b 2 H,H 2
2
3
6
3
2
50.5 Hz, J = 28.0 Hz, J = 7.3 Hz, CF ), 111.8 (C , Ar-N), 109.1 (tt,
C,F
C,P
2
1
JC,F = 250.0 Hz, 2JC,F = 36.0 Hz, HCF ), 108.9 (tt, J = 250.0 Hz, J
1
2
=
13
C NMR (100.62 MHz, CDCl ): = 153.0 (C , Ar-N), 139.3 (d, 3JC,P
4
2
C,F
C,F
=
3
2
2
3
6.0 Hz, HCF ), 62.4 (td, JC,F = 30.0 Hz, JC,P = 6.6 Hz, C H ), 62.1 (td,
1
4
2
a
2
15.4 Hz, C , Ar-N), 134.4 (C , Ph-C), 129.2 (d, JC,P = 2.6 Hz, C , Ph-C),
i m
2
JC,F = 30.0 Hz, JC,P = 6.6 Hz, C H ), 56.1 (d, 1J = 154.4 Hz, CH), 17.1
2
b
2
C,P
128.9 (d, J = 3.3 Hz, C , Ph-C), 127.9 (d, J = 6.3 Hz, C , Ph-C), 116.1
5
3
C,P p C,P o
(
CH3).
(C2,6, Ar-N), 115.7 (C3,5, Ar-N), 113.8 (ttd, J = 250.0 Hz, J = 27.8 Hz,
1
2
C,F
C,F
1
9
3
JC,P = 7.3 Hz, CF ), 113.6 (ttd, J = 250.0 Hz, J = 27.8 Hz, 3JC,P = 7.5
1
2
F NMR (376.50 MHz, CDCl ): = –137.02, –137.21, –137.71, –138.07
3
2 C,F C,F
2
1
2
1
(m, J = 53.0 Hz, 4 F, HCF ), –124.27, –124.52, –124.69, –125.13 (m,
Hz, CF ), 109.1 (tt, J = 250.8 Hz, J = 27.6 Hz, HCF ), 108.9 (tt, J
=
C,F
F,H
2
2
C,F
C,F
2
2
2
4
F, CF2).
250.0 Hz, J = 35.4 Hz, HCF ), 64.0 (CH Me), 62.7 (td, J = 30.0 Hz,
C,F
2
2
C,F
2
2
2
31
J
C,P = 6.5 Hz, C H ), 62.3 (td, JC,F = 30.5 Hz, JC,P = 6.8 Hz, C H ), 57.5 (d,
a
2
b
2
P NMR (161.98 MHz, CDCl ): = 25.4.
3
1
JC,P = 155.2 Hz, CH), 15.0 (CH3).
Anal. Сalcd for C20H20F NO P (505.339): С, 47.54; Н, 3.99; N, 2.77.
8
3
19
F NMR (376.50 MHz, CDCl ): = –137.17, –137.37, –138.01, –138.34
Found: C, 47.92; Н, 3.71 N, 2.37.
3
2
(m, J = 53.0 Hz, 4 F, HCF ), –124.40, –124.68, –124.96, –125.33 (m,
F,H
2
4
F, CF2).
Bis(2,2,3,3-tetrafluoropropyl) [(Naphthalene-1-ylamino)(phe-
nyl)methyl]phosphonate (3i)
31
P NMR (161.98 MHz, CDCl ): = 26.0.
3
White solid; yield: 541 mg (~100%); mp 69–70 °C.
Anal. Сalcd for C21H F NO P (535.365): С, 47.11; Н, 4.14; N, 2.62.
22 8 4
Found: C, 47.50; Н, 3.75; N, 2.65.
IR (KBr): 3429, 3319, 3064, 3010, 2972, 2925, 2902, 2233, 1957, 1625,
1
9
1
584, 1530, 1493, 1458, 1406, 1352, 1285, 1246, 1191, 1123, 1064,
–1
Bis(2,2,3,3-tetrafluoropropyl) [(4-Hydroxy-3-methoxyphenyl)-
63, 935, 888, 816, 784, 698, 674, 646, 596, 557, 496, 456, 430 cm
.
(phenylamino)methyl]phosphonate (3k)
3
5
H NMR (400.13 MHz, CDCl ): = 8.00 (d, J = 8.3 Hz, 1 H, H , naph-
3
H,H
3
8
6
Purified by Method B; yield: 516 mg (96%); yellow oil.
thyl), 7.82 (d, J = 7.5 Hz, 1 H, H , naphthyl), 7.56–7.54 (m, 1 H, H ,
naphthyl), 7.56–7.51 (m, 2 H, H , C H ), 7.52–7.49 (m, 1 H, H , naphth-
H,H
7
IR (film): 3527, 3329, 3051, 3016, 2966, 2847, 2568, 2406, 2251,
o
6
5
yl), 7.42–7.38 (m, 2 H, H , C H ), 7.37–7.35 (m, 1 H, H , C H ), 7.32 (d,
2061, 1934, 1863, 1679, 1602, 1512, 1459, 1435, 1378, 1272, 1240,
m
6
5
p
6
5
3
4
3
3
–1
JH,H = 8.3 Hz, 1 H, H , naphthyl), 7.22 (dd, J = 8.3 Hz, J = 7.6 Hz, 1
1210, 1111, 1060, 943, 877, 836, 755, 687, 631, 547, 512, 474 cm
.
H,H
H,H
©
2020. Thieme. All rights reserved. Synthesis 2020, 52, A–J