PHOSPHORUS, SULFUR, AND SILICON
277
3
(m, 6H, 3NCH2), 3.15 (m, 2H, NCH2), 4.17 (q, 2H, JHH
=
m.p. = 92°C. 1H NMR (CDCl3): δ = 1.26 (t, 3H, 3JHH = 7 Hz,
2
3
3
2
7 Hz, OCH2), 4.62 (m, 1H, JHP = 23 Hz, JHF = 8 Hz, CH), CH3), 4.19 (q, 2H, JHH = 7 Hz, CH2), 5.14 (ddq, 1H, JHP
=
=
and 5.75 (dd, 1H, 3JHH = 10 Hz, 3JHP = 4 Hz, NH). 19F NMR 21 Hz, 3JHH = 10 Hz, 3JHF = 8 Hz, CH), 5.49 (dd, 1H, 3JHH
(CDCl3): δ = −69.77 (dd, 3JFH = 8.5 Hz, 3JFP = 4 Hz,). 31P-{H} 10 Hz, 3JHP = 2 Hz, NH), 7.20 (m, 6H, Ph), and 7.33 (m, 4H, Ph).
NMR (CDCl3): δ = 23.11 (q, 3JPF = 4 Hz). 13C NMR (CDCl3): 19F NMR (CDCl3): δ = −70.13 (t, 3JFH ∼ JFP 7.8 Hz). 31P-{H}
3
δ = 13.79 (d, 3JCP = 3 Hz, NCH2CH3), 14.29 (d, 3JCP = 2 Hz, NMR (CDCl3): δ = 5.78 (q, 3JPF = 7.5 Hz). 13C NMR (CDCl3):
NCH2CH3), 14.46 (OCH2CH3), 38.24 (d, 2JCP = 4 Hz, NCH2), δ = 14.30 (CH3), 51.12 (dq, 1JCP = 160 Hz, 2JCF = 32 Hz, CHP),
38.69 (d, 2JCP = 5 Hz, NCH2), 49.05 (dq, 1JCP = 120 Hz, 2JCF
31 Hz, CHP), 61.94 (OCH2), 124.11 (qd, 1JCF = 289 Hz, 2JCP
=
=
62.51 (OCH2), 120.16 (d, 4JCP = 4 Hz, C2,6Ph), 120.31 (d, 4JCP
= 4 Hz, C2,6Ph), 122.71 (qd, 1JCF = 284 Hz, 2JCP = 9 Hz, CF3),
8 Hz, CF3), and 155.89 (d, 3JCP = 7 Hz, C=O). Anal. Calc. for 125.80, 125,88, 129.83, 129,91, 149.45 (d, JCP = 9 Hz, C1Ph),
2
C13H27F3N3O5P: C, 43.21; H, 7.53; N, 11.63. Found: C, 43.15; 149.73 (d, 2JCP = 8 Hz, C1Ph), and 155.56 (d, 3JCP = 6 Hz, C=O).
H, 7.80; N, 11.55.
Anal. Calc. for C17H17F3NO5P: C, 50.62; H, 4.25; N, 3.47. Found:
C, 50.85; H, 4.09; N, 3.59.
O-Ethyl (1-ethoxycarbonylamino-2,2,2-
trifluoroethyl)phenylphosphinate 4c
O,O-Diphenyl 1-ethoxycarbonylamino-2,2,2-
O,O-Diethyl phenylphosphinite 3c (0.289 g, 1.46 mmol) was trichloroethylphosphonate 4f
added to a solution of chloride 2a (0.3 g, 1.46 mmol) in benzene
Method A
(4 mL). The mixture was stirred at room temperature for 18 h,
To a stirred solution of chloride 2b (0.3 g, 1.18 mmol) diethyl
the solvent was evaporated in vacuo. The residue was crystal-
ether (4 mL) was added dropwise a solution of triethylamine
(0.165 mL, 1.18 mmol) in diethyl ether (0.5 mL). After 10 min,
the precipitate was filtered off and diphenylphosphite (0.44 mL,
2.36 mmol) was added to a filtrate. After 18 h, the precipitate was
isolated by filtration and crystallized from benzene/petroleum
ether (1:1). Yield 0.41 g (77%); m.p. = 147°C.
lized from petroleum ether to afford 4c as diastereomeric mix-
1
ture (A/B 2.3:1). Yield 0.26 g (55%). H NMR (CDCl3): δ =
3
3
1.11 (t, JHH = 7 Hz, POCH2CH3) (A), 1.25 (t, JHH = 7 Hz,
POCH2CH3) (B), 1.37 (t, 3H, 3JHH = 7 Hz, COOCH2CH3), 3.99
3
(q, 2H, JHH = 7 Hz, COOCH2), 4.20 (m, 2H, POCH2), 4.75
(m, 1H, CH), 5.33 (d, 3JHH = 11 Hz, NH) (A), 5.59 (d, 3JHH
=
11 Hz, NH) (B), and 7.5–7.9 (m, 5H, Ph). 19F NMR (CDCl3): δ
= −68.57 (A), −68.82 (B) (A/B 2.3:1). 31P NMR (CDCl3): δ =
31.64 (A), 30.49 (B) (A/B 2.3:1). Anal. Calc. for C13H17F3NO4P:
C, 46.03; H, 5.05; N, 4.13. Found: C, 45.76; H, 4.95; N, 3.86.
Method B
A solution of diphenylphosphite (0.87 ml, 4.57 mmol) in diethyl
ether (2 mL) was added dropwise to a stirred solution of ethyl
(2,2,2-trichloroethylidene)carbamate 6b (1.0 g, 4.57 mmol) in
diethyl ether (10 mL). After 18 h, the precipitate was filtrated,
dried in vacuo and crystallized from benzene/petroleum ether
Diphenyl(1-ethoxycarbonylamino-2,2,2-
trifluoroethyl)phosphine oxide 4d
1
(1:1). Yield 1.146 g (57%); m.p. = 147°C. H NMR (CDCl3):
O-Ethyl diphenyl phosphinite 3d (0.127 g, 0.97 mmol) was
added to a solution of chloride 2a (0.2 g, 0.97 mmol) in ben-
zene (2 mL). The precipitate was isolated by filtration and dried
in vacuo. Yield 0.16 g (60%); m.p. = 208°C. 1H NMR (CDCl3):
δ = 1.12 (t, 3H, 3JHH = 7 Hz, CH3), 4.04 (q, 2H, 3JHH = 7 Hz,
CH2), 5.27 (m, 1H, 2JHP = 18 Hz, 3JHF = 8.5 Hz, CH), 5.86 (d,
δ = 1.24 (t, 3H, 3JHH = 7 Hz, CH3), 4.19 (q, 2H, 3JHH = 7 Hz,
2
3
CH2), 5.37 (dd, 1H, JHP = 20 Hz, JHH = 10 Hz, CHP), 5.82
(d, 1H, 3JHH = 10 Hz, NH), 7.17 – 7.24 (m, 4H, Ph), and 7.30–
7.37 (m, 6H Ph). 31P NMR (CDCl3): δ = 6.9 (d, 2JPH = 20 Hz).
13C NMR (CDCl3): δ = 14.41 (CH3), 62.58 (CH2), 64.10 (d,
1JCP = 164 Hz, CHP), 96.40 (d, JCP = 17 Hz, CCl3), 120.23
2
3
1H, JHH = 11 Hz, NH), 7.52 (m, 6H, Ph), and 7.85 (m, 4H,
(d, 3JCP = 4 Hz, C2,6Ph), 120.49 (d, 3JCP = 4 Hz, C2,6Ph), 125.65,
3
3
Ph). 19F NMR (CDCl3): δ = −67.22 (dd, JFH = 8.5 Hz, JFP
= 1.5 Hz). 31P NMR (CDCl3): δ = 27.5. 13C NMR (CDCl3): δ
= 14.28 (CH3), 52.31 (dq, 2JCF = 30 Hz, 1JCP = 147 Hz, CH),
125.78, 129.82, 129.94 (Ph), 149.75 (d, 2JCP = 9 Hz, C1Ph), 150.12
2
(d, JCP = 9 Hz, C1Ph), and 155.46 (C=O). Anal. Calc. for
C17H17Cl3NO5P: C, 45.11; H, 3.79; Cl, 23.50. Found: C, 45.15;
H, 3.58; Cl, 23.39.
1
2
62.27 (CH2), 128.28 (qd, JCF = 277 Hz, JCP = 6 Hz, CF3),
128.8 (d, 2JCP = 12 Hz, C2,6Ph), 128.9 (d, 2JCP = 12 Hz, C2,6Ph),
129.2 (d, 1JCP = 97 Hz, C1Ph), 131.0 (d, 3JCP = 10 Hz, C3,5Ph),
131.30 (d, 3JCP = 10 Hz, C3,5Ph), 132.76 (d, 3JCP = 2 Hz, C4Ph),
132.87 (d, 3JCP = 2 Hz, C4Ph), and 155.8 (C=O). Anal. Calc. for
C17H17F3NO3P: C, 54.99; H, 4.62; N, 3.77. Found: C, 54.87; H,
4.52; N, 3.81.
O-Propyl (1-ethoxycarbonylamino-2,2,2-
trichloroethyl)phenylphosphinate 4g
A mixture of 6 (0.1 g, 0.458 mmol), 7b (0.084 g, 0.458 mmol)
and one drop of triethylamine was heated at 90°C for 2 h.
After cooling to room temperature the mixture was tritu-
rated with petroleum ether and crystallized from ethanol/water
O,O-Diphenyl 1-ethoxycarbonylamino-2,2,2-
trifluoroethylphosphonate 4e
(1:1) to afford phosphinate 4 g as diastereomeric mixture (A/B
1
Triethylamine (0.202 mL, 1.46 mmol) was added to a solution 2.3:1). Yield 0.095 g (52%); m.p. = 129°C. H NMR (CDCl3):
of chloride 2a (0.296 g, 1.46 mmol) in benzene (4 mL). After δ = 0.97 (m, 3H, COOCH2CH3), 1.11 (t, CH2CH2CH3)
3
10 min, the precipitate was filtered off and diphenyl phosphite (B), 1.28 (t, JHH = 7 Hz, CH2CH2CH3) (A), 1.24 (m, 2H,
(0.273 mL, 1.46 mmol) was added to a filtrate. After 20 h, the OCH2CH2CH3), 4.06 (m, 2H, POCH2CH2), 4.21 (m, 2H,
3
precipitate was isolated by filtration, triturated with petroleum COOCH2), 5.03 (m, 1H, CH) 5.63 (d, JHH = 9 Hz, NH) (B),
ether, washed with water and dried on the air. Yield 0.13 g (22%); 5.91 (d, JHH = 9 Hz, NH) (A), and 7.5–7.9 (m, 5H, Ph). 31P
3