L. Delain-Bioton, D. Villemin, P.-A. Jaffrès
FULL PAPER
(153 mg, 0.6 mmol) and alkyne 12 (189 mg, 0.92 mmol) at room
temperature. Purification was effected by chromatography on silica
gel (dichloromethane/methanol, 85:15). Yield: 188 mg (97%) of a
3.02 (t, 2J = 15 Hz, 2 H, CH2CϵC), 4.02–4.28 (m, 8 H,
4ϫCH3CH2O), 7.05 (d, 3J = 7 Hz, 2 H, 2ϫCHCCH3), 7.30 (d, 3J
= 7 Hz, 2 H, 2ϫCHCCϵC) ppm. 31P NMR (101.25 MHz,
CDCl3): δ = 26.50 ppm. 13C NMR (62.9 MHz, CDCl3): δ = 16.8
yellow oil. IR (neat): ν = 1236 (P=O), 1014, 964 (P–O) cm–1. 1H
˜
3
NMR (250 MHz, CDCl3): δ = 1.37 (t, J = 7 Hz, 6 H, 2ϫCH3), (t, 3J = 3 Hz, 4ϫCH3), 17.1 (t, 2J = 6 Hz, CH3), 21.8 (s, CH3),
3.94 (d, 2J = 10 Hz, 2 H, PCH2O), 4.21 (m, 4 H, 2ϫCH3CH2OP), 24.4 (t, J = 4 Hz, CH2CϵC), 40.9 (t, J = 135 Hz, PCP), 63.3 (d,
3
1
4.55 (d, 2J = 2 Hz, 2 H, OCH2CϵCH), 7.59 (d, 3J = 9 Hz, 2 H, 3J = 4 Hz, 4ϫPOCH2), 83.7 (s, CϵCCar), 84.8 (s, CϵCCar), 120.9
2ϫCHCCϵC), 8.20 (d, J = 9 Hz, 2 H, 2ϫCHCNO2) ppm. 31P
(s, CCϵC), 129.3 (s, 2ϫCHCCH3), 131.7 (s, 2ϫCHCCϵC), 138.2
3
NMR (101.25 MHz, CDCl3):
(62.9 MHz, CDCl3): δ = 16.8 (d, J = 6 Hz, 2ϫCH3), 61.0 (d, J
δ
3
=
22.80 ppm. 13C NMR (s, CCH3) ppm. MS (16 eV): m/z (%) = 431 (28) [M + H]+, 404
2
(14), 403 (100), 375 (62), 347 (23), 319 (8). HRMS (ES-TOF): calcd.
= 13 Hz, 2ϫCH2OP), 63.0 (d, 3J = 6 Hz, OCH2), 63.9 (d, 1J = for C20H33O6P2 [M + H]+ 431.1752; found 431.1743.
167 Hz, PCH2O), 86.0 (s, CϵCCar), 89.5 (s, CϵCCar), 124.0 (s,
Tetraethyl {Methyl-[3-(4-nitrophenyl)prop-2-ynyl]methylene}diphos-
phonate (14b): Method A was employed with 1-bromo-4-nitroben-
zene (153 mg, 0.6 mmol) and alkyne 14 (312 mg, 0.92 mmol) at
room temperature. Purification was effected by chromatography on
2ϫCHCNO2), 129.4 (s, CarCϵC), 132.9 (s, 2ϫCHCCϵC), 147.7
(s, CNO2) ppm. MS (10 eV): m/z (%) = 329 (13) [M + H]+, 328
(100) [M]+, 300 (30), 272 (21), 181 (5), 178 (10), 160 (38), 151 (9).
HRMS (ES-TOF): calcd. for C14H18NO6PNa [M + Na]+ 350.0769;
silica gel (dichloromethane/methanol, 80:20). Yield: 251 mg (91%)
found 350.0776.
of a yellow oil. IR (neat): ν = 1235 (P=O), 1013, 962 (P–0) cm–1.
˜
Diethyl {[3-(Pyridin-4-yl)prop-2-ynyloxy]methyl}phosphonate (12c): 1H NMR (250 MHz, CDCl3): δ = 1.35 (t, 3J = 7 Hz, 12 H,
Method C was employed with 4-bromopyridine hydrochloride
(108 mg, 0.6 mmol) and alkyne 12 (156 mg, 0.76 mmol) at 120 °C.
4ϫCH3CH2O), 1.53 (t, 3J = 16 Hz, 3 H, CH3), 2.92 (t, 2J = 15 Hz,
3
2 H, CH2CϵC), 4.02–4.28 (m, 8 H, 4ϫCH3CH2O), 7.45 (d, J =
3
Yield: 108 mg (64%) of a yellow oil. IR (neat): ν = 1230 (P=O),
9 Hz, 2 H, 2ϫCHCCϵC), 8.15 (d, J = 9 Hz, 2 H, 2ϫCHCNO2)
˜
1
1100 (C–O), 1027, 960 (P–O) cm–1. H NMR (250 MHz, CDCl3): ppm. 31P NMR (101.25 MHz, CDCl3): δ = 25.20 ppm. 13C NMR
δ = 1.36 (t, 3J = 7 Hz, 6 H, 2ϫCH3), 3.95 (d, 2J = 9 Hz, 2 H,
PCH2O), 4.23 (m, 4 H, 2ϫCH2OP), 4.53 (s, 2 H, OCH2CϵCH),
7.30 (d, 3J = 6 Hz, 2 H, 2ϫCHCCH3), 8.59 (d, 3J = 6 Hz, 2 H,
(62.9 MHz, CDCl3): δ = 16.3–16.9 (t, J = 3 Hz, 4ϫCH3), 17.0 (t,
3
2J = 6 Hz, CH3), 24.3 (t, 3J = 4 Hz, CH2CϵC), 40.3 (t, 1J = 135 Hz,
3
PCP), 63.0 (d, J = 4 Hz, 4ϫPOCH2), 81.8 (s, CϵCCar), 91.6 (s,
2ϫCHCCϵC) ppm. 31P NMR (101.25 MHz, CDCl3): δ = 22.8 CϵCCar), 123.5 (s, 2ϫCHCNO2), 130.6 (s, CCϵC), 132.2 (s,
ppm. 13C NMR (62.9 MHz, CDCl3): δ = 15.3 (d, 3J = 5 Hz, 2ϫCHCCϵC), 146.7 (s, CNO2) ppm. MS (20 eV): m/z (%) = 462
2ϫCH3), 59.4 (d, 2J = 14 Hz, 2ϫCH3CH2OP), 61.4 (d, 3J = 6 Hz,
(20) [M + H]+, 434 (29), 406 (47), 378 (70), 350 (100). HRMS (ES-
1
OCH2), 62.3 (d, J = 166 Hz, PCH2O), 83.6 (s, CϵCCar), 87.5 (s,
TOF): calcd. for C19H30NO8P2 [M
462.1440.
+
H]+ 462.1447; found
CϵCCar), 124.5 (s, 2ϫCH), 129,4 (s, CarCϵC), 148.6 (s, 2ϫCHN)
ppm. MS (12 eV): m/z (%) = 299 (4) [M + 2H]+, 298 (38) [M +
H]+, 165 (100), 137 (22), 127 (55), 109 (20). HRMS (ES-TOF):
calcd. for C13H19NO4P [M + H]+ 284.1052; found 284.1061.
Tetraethyl {Methyl[3-(1,10-phenanthrolin-3-yl)prop-2-ynyl]methyl-
ene}diphosphonate (14c): Method B was employed with 3-bromo-
1,10-phenanthroline (197 mg, 0.6 mmol) and alkyne 14 (312 mg,
Diethyl {[3-(1,10-Phenanthrolin-3-yl)prop-2-ynyloxy]methyl}phos- 0.92 mmol) at reflux. Purification was effected by chromatography
phonate (12d): Method B was employed with 3-bromo-1,10-phen-
anthroline (197 mg, 0.6 mmol) and alkyne 12 (189 mg, 0.92 mmol)
at reflux. A washing step with KCN was added to the workup.
Purification was effected by chromatography on silica gel (dichloro-
on silica gel (dichloromethane/methanol, 90:10), affording com-
pound 14c (248 mg, 80% yield, yellow solid) and compound 14d
(30 mg, 9% yield). IR (neat): ν = 2235 (CϵC), 1235 (P=O), 1097
˜
1
(C–O), 1014, 962 cm–1. H NMR (250 MHz, CDCl3): δ = 1.29 (t,
3
methane/methanol, 90:10). Yield: 180 mg (78%) of an orange solid.
3J = 7 Hz, 12 H, 4ϫCH3CH2O), 1.57 (t, J = 16 Hz, 3 H, CH3),
1
IR (neat): ν = 1226 (P=O), 1099 (C–O), 1024, 957 (P–O) cm–1. H
3.05 (t, 2J = 15 Hz, 2 H, CH2CϵC), 4.05–4.26 (m, 8 H,
˜
NMR (250 MHz, CDCl3): δ = 1.38 (t, J = 7 Hz, 6 H, 2ϫCH3), 4ϫCH3CH2O), 7.48 (dd, J = 8 Hz, JHH = 4 Hz, H8), 7.59 (d, J
3
3
3
3
4.01 (d, J = 9 Hz, 2 H, PCH2O), 4.23 (m, 4 H, 2ϫCH2OP), 4.62 = 9 Hz, H6), 7.65 (d, 3J = 9 Hz, H5), 8.10 (d, 3J = 9 Hz, H7), 8.16 (s,
2
(s, 2 H, OCH2CϵCH), 7.65 (dd, J = 8 Hz, J = 4 Hz, H8), 7.75 H4), 9.03 (m, 2 H, H2, H9) ppm. 31P NMR (101.25 MHz, CDCl3): δ
3
3
(d, 3J = 9 Hz, H6), 7.82 (d, 3J = 9 Hz, H5), 8.26 (d, 3J = 9 Hz, H7),
8.31 (s, H4), 9.19 (s, 2 H, H2, H9) ppm. 31P NMR (101.25 MHz,
CDCl3): δ = 22.16 ppm. 13C NMR (62.9 MHz, CDCl3): δ = 16.1
= 24.5 ppm. 13C NMR (62.9 MHz, CDCl3): δ = 16.4 (t, 3J = 3 Hz,
2
3
4ϫCH3), 16.9 (t, J = 6 Hz, CH3), 24.24 (t, J = 4 Hz, CH2CϵC),
1
3
40.3 (t, J = 135 Hz, PCP), 62.9 (m, J = 4 Hz, 4ϫPOCH2), 80.2
3
2
3
(d, J = 6 Hz, 2ϫCH3), 60.4 (d, J = 9 Hz, 2ϫCH2OP), 62.3 (d,
3J = 6 Hz, OCH2), 63.2 (d, 1J = 144 Hz, PCH2O), 84.2 (s, CϵCH),
87.9 (s, CϵCH), 118.9 (s, C3), 123.0 (s, C8), 125.6 (s, C6), 127.1 (s,
(s, CϵCCar), 90.1 (t, J = 5 Hz, CϵCCar), 119.8 (s, C3), 123.1 (s,
C8), 125.3 (s, C6), 127.1 (s, C5), 127.6 (s, C12), 128.7 (s, C13), 135.9
(s, C7), 137.9 (s, C4), 144.4 (s, C11), 146.02 (s, C14), 150.4 (s, C9),
C5), 127.2 (s, C12), 128.7 (s, C13), 135.7 (s, C7), 138.2 (s, C4), 144.8 152.0 (s, C2) ppm. MS (20 eV): m/z (%) = 519 (20) [M + H]+, 491
(s, C11), 145.5 (s, C14), 150.3 (s, C9), 151.7 (s, C2) ppm. MS (12 eV):
(9), 463 (8), 445 (22), 417 (88), 389 (50), 381 (100), 353 (68), 325
m/z (%) = 386 (8) [M + H]+, 385 (25) [M]+, 357 (17), 329 (8), 311 (41), 309 (37). HRMS (ES-TOF): calcd. for C25H33N2O6P2 [M +
(45), 281 (15), 219 (17), 217 (100). HRMS (ES-TOF): calcd. for H]+ 519.1814; found 519.1793.
C20H22N2O4P [M + H]+ 385.1317; found 385.1306.
Octaethyl (Dec-4,6-diynyl)-2,2,9,9-tetraphosphonate (14d): IR
Tetraethyl {Methyl[3-(p-tolyl)prop-2-ynyl]methylene}diphosphonate (neat): ν = 1233 (P=O), 1012, 943 (P–O) cm–1. 1H NMR (250 MHz,
˜
3
3
(14a): Method A was employed with 4-iodotoluene (130 mg,
0.6 mmol) and alkyne 14 (312 mg, 0.92 mmol) at room tempera-
ture. Purification was effected by chromatography on silica gel
(dichloromethane/methanol, 85:15). Yield: 232 mg (90%) of a
CDCl3): δ = 1.34 (t, J = 7 Hz, 16 H, 8ϫCH3CH2O), 1.53 (t, J =
16 Hz, 6 H, 2ϫCH3), 2.89 (t, 2J = 15 Hz, 4 H, 2ϫCH2CϵC),
4.17–4.22 (m, 24 H, 8ϫCH3CH2O) ppm. 31P NMR (101.25 MHz,
CDCl3): δ = 26.50 ppm. 13C NMR (62.9 MHz, CDCl3): δ = 16.4
(slarge, 8ϫCH3), 23.8 (t, 2J = 6 Hz, 2ϫCH3), 23.8 (t, 3J = 4 Hz,
colourless oil. IR (neat): ν = 1235 (P=O), 1015, 960 (P–O) cm–1.
˜
1H NMR (250 MHz, CDCl3): δ = 1.33 (t, 3J = 7 Hz, 12 H,
4ϫCH3CH2O), 1.62 (t, 3J = 16 Hz, 3 H, CH3), 2.33 (s, 3 H, CH3),
CH2CϵC), 40.1 (t, J = 135 Hz, PCP), 63.0 (m, 8ϫPOCH2), 68.1
1
(s, CH2CϵC), 72.8 (t, 3J = 10 Hz, 2ϫCH2CϵC) ppm. MS (21 eV):
1284
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Eur. J. Org. Chem. 2007, 1274–1286