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Typical Procedure
for the Preparation of Compounds 4-7
A mixture
of diketone 3 (10.0 mmol), phosphorus reagent [11.0
mmol in the case of diethyl phosphite or ethyl(methyl)phosphonite,
15 mmol in the case of ethyl(phenyl)phosphonite, or 20 mmol in the
case of diphenylphosphine oxide], and triethylborate (1.60
g, 11.0 mmol in the case of phosphite and phosphonites or 2.92 g, 20.0
mmol in the case of diphenylphosphine oxide) was refluxed in MeCN
(20 mL) for the respective time (Table
[¹]
). All volatile materials
were removed in vacuo, and the residue was dissolved in Et2O
(30 mL). The ether solution was washed with H2O (10 mL)
and 10% solution of Na2CO3 (3 × 10
mL). For compounds 6 and 7 a
sat. solution of NaHCO3 was used. Et2O was
removed, the crude product was dissolved in CHCl3 (10
mL) and filtered through a layer of silica (3 sm). The solvent was
evaporated, and the residue was dried in vacuo for 12 h. For compounds 6 and 7, the products
were purified by column chromatography (EtOAc-hexane = 1:2).
Data for Diethyl 1-Hydroxy-3-(4-nitrophenyl)-3-oxo-1-(trifluoromethyl)propylphosphonate (4b)
Yellowish viscous oil. ¹H
NMR (200 MHz, CDCl3): δ = 1.23 (t,
3 H, Me, J = 7.1
Hz), 1.27 (t, 3 H, Me, J = 7.1
Hz), 3.21 (dd, 1 H, J
Ha-Hb = 16.1
Hz, J
Ha-P = 18.6
Hz, CHH), 3.82 (dd, 1 H, J
Ha-Hb = 16.1
Hz, J
Hb-P = 7.3
Hz, CHH), 4.10-4.36 (m, 4 H,
2 OCH2), 6.74 (d, 1 H, J
H-P = 8.3
Hz, OH) 7.61-7.66 (m, 2 H, Ar), 7.88-7.93 (m,
2 H, Ar). ¹9F NMR (188 MHz, CDCl3,
C6F6): δ = 88.96
(d, J
F-P = 5.2
Hz, CF3). ³¹P-¹H decoupled
(81 MHz, CDCl3, 85% H3PO4): δ = 16.68
(q,
J
P-F = 5.2
Hz). ¹³C NMR (50 MHz, CDCl3) δ = 16.13
(d,
³
J
C-P = 5.2
Hz, Me), 38.64 (s, CH2), 63.58 (d, ²
J
C-P = 7.4
Hz, OCH2), 63.63 (d, ²
J
C-P = 7.4
Hz, OCH2), 75.58 (dq,
¹
J
C-P = 164.6
Hz, ²
J
C-F = 29.0
Hz), 124.41 (qd, CF3, ¹
J
C-F = 285.4
Hz, ²
J
C-P = 12.6
Hz), 124.42, (CH, Ar), 130.87 (CH, Ar), 143.03 (Ar), 150.70 (Ar),
195.94 (d, ³
J
C-P = 8.5 Hz,
C=O). Anal. Calcd for C14H17NPF3O7:
C, 42.12; H, 4.29; F, 14.28. Found: C, 42.31; H, 4.17; F, 14.42.
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General Procedure
for the Preparation of Compounds 8-10
To
a vigorously stirred solution of phosphonate 4 or phosphinate 5 or 6 (5.0 mmol)
and dry pyridine (0.79 g, 10 mmol) in dry CH2Cl2 (20
mL) a solution of TFAA (2.10 g, 10 mmol) in dry CH2Cl2 (20
mL) was added dropwise at 0 ˚C. The reaction mixture was
stirred for 4 h at the same temperature, warmed to r.t., washed
with cold H2O (ca. 5 ˚C, 3 × 10
mL), and filtered through layer of silica (4 sm). The solvent was
evaporated and residue was dried in vacuo for 12 h.
Data for Diethyl 3-(4-Nitrophenyl)-3-oxo-1-(trifluoromethyl)prop-1-enylphosphonate
(8b)
Yellow viscous oil; E/Z = 10:1.
Compound (
Z
)-8b: ¹H NMR (200 MHz,
CDCl3): δ = 1.27
(t, 6 H, 2 Me, J = 7.1
Hz), 4.01-4.17 (m, 4 H, 2 OCH2), 7.57 (dq, 1
H, J
H-P = 39.0
Hz, J
H-F = 1.5
Hz, =CH), 8.02-8.06 (m, 2 H, Ar), 8.31-8.36
(m, 2 H, Ar). ¹9F NMR (188 MHz, CDCl3,
C6F6): δ = 99.27
(s). ³¹P-¹H
coupled (81 MHz, CDCl3, 85% H3PO4): δ = 6.67
(dm, J
P-H = 39.0
Hz). ³¹P-¹H decoupled
(81 MHz, CDCl3, 85% H3PO4): δ = 6.67
(q,
J
P-F = 2.5
Hz). ¹³C NMR (50 MHz, CDCl3): δ = 16.00
(d, ³
J
C-P = 7.1
Hz, Me), 63.80 (d, ²
J
C-P = 5.7
Hz, OCH2), 121.65 (qd, CF3, ¹
J
C-F = 275.5
Hz, ²
J
C-P = 15.5
Hz), 124.06 (CH, Ar), 129.00 (dq, ¹
J
C-P = 182.3
Hz, ²
J
C-F = 32.5
Hz), 129.82, (CH, Ar), 139.48 (Ar), 147.39 (m, =CH), 150.82
(Ar), 190.20 (d, ³
J
C-P = 7.1
Hz, C=O).
Compound (
E
)-8b: ¹H
NMR (200 MHz, CDCl3): δ = 1.41
(t, 6 H, 2 Me, J = 7.1
Hz), 4.19-4.35 (m, 4 H, 2 OCH2), 7.77 (d, 1
H, J
H-P = 24.0
Hz, =CH), 8.02-8.06 (m, 2 H, Ar), 8.31-8.36
(m, 2 H, Ar). ¹9F NMR (188 MHz, CDCl3,
C6F6): δ = 104.36
(d, J
F-P = 5.5
Hz). ³¹P-¹H
decoupled (81 MHz, CDCl3, 85% H3PO4): δ = 9.06
(q, J
P-F = 5.2
Hz). ¹³C NMR (50 MHz, CDCl3): δ = 16.20
(d, ³
J
C-P = 7.0
Hz, Me), 64.09 (d, ²
J
C-P = 5.7
Hz, OCH2), 124.26 (CH, Ar), 130.04, (CH, Ar), 148.66
(m, =CH). Signals of carbon without hydrogen were not found.
Anal. Calcd for C14H15NPF3O6:
C, 44.11; H, 3.97; F, 14.95. Found: C, 44.03; H, 3.75; F, 15.10.
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