K. M. Armstrong, P. Kilian
FULL PAPER
spectroscopic numbering scheme, see Scheme 6. 31P{1H} NMR
Independent Synthesis of 2,4-Di-tert-butylphenyl Phosphate: 2,4-di-
(109.4 MHz, CDCl3): δ = –60.0 (s) ppm. 1H NMR (270.2 MHz, tert-butylphenyl phosphite (5.00 g, 0.0078 mol, synthesized accord-
CDCl3): δ = 1.31 (s, 9 H, 8-tBu), 1.44 (s, 9 H, 7-tBu), 7.21 (dd, J
= 8.9 and 2.1 Hz, 1 H, 5-H), 7.41 (≈t, J = 2.4 Hz, 1 H, 3-H), 7.66
(dd, J = 8.9 and 2.1 Hz, 1 H, 6-H) ppm. 13C{1H} NMR (67.9 MHz,
ing to the method of Akbarali.[25]), 30% hydrogen peroxide solu-
tion (5.8 mL, 0.051 mol) and water (20 mL) were added to a round-
bottomed flask and stirred for 48 h at room temperature. The re-
CDCl3): δ = 30.4 (s, 7-CH3), 31.5 (s, 8-CH3), 34.7 (s, 7-Cq), 34.9 (s, sulting mixture after evaporation of volatiles was found to contain
3
8-Cq), 119.4 [d, J(C,P) = 4.0 Hz, 6-CH], 124.3 (s, 5-CH), 125.0 (s, 2,4-di-tert-butylphenyl phosphate by 31P{1H} NMR spectroscopy
3-CH), 139.3 [d, 2J(C,P) = 9.4 Hz, 1-Cq], 147.2 [d, 3J(C,P) = 7.7 Hz,
(109.4 MHz, CDCl3): δ = –19.9 (s) ppm.
2-C ], 148.1 (s, 4-C ) ppm. IR (KBr disc): ν = 2954 (vs, νCH), 1494
˜
q
q
Iron(III) 2,2,6,6-Tetramethyl-3,5-heptanedioneate (1): 2,2,6,6-tet-
ramethyl-3,5-heptanedione (9.90 g, 0.054 mol), iron(III) chloride
(2.92 g, 0.018 mol) and sodium acetate (4.42 g, 0.054 mol) were dis-
solved in a 50:50 ethanol/water mixture (50 mL). The solution was
heated to 60 °C for 1 h with stirring. An orange precipitate formed
on cooling with an ice bath. The solid was collected by filtration
and washed with water (25 mL). Drying the solid in vacuo yielded
1 (10.34 g, 95%) as an orange powder. The IR spectrum and melt-
ing point of the compound (163–164 °C) were found to be in excel-
lent agreement with those in the literature.[40,21]
(s), 1273 (m, νP=O), 1182 (s), 1104 (m), 1079 (m), 991 (s), 960 (vs),
552 (vs), 495 (vs) cm–1. MS (ES+, solution in methanol): m/z =
1488.1 [(M – I + MeO)3 + Na]+, 999.5 [(M – I + MeO)2 + Na]+,
977.4 [(M – I + MeO)2 + H]+, 511.2 [M – I + MeO + Na]+, 489.3
[M – I + MeO + H]+, 433.2 [M – I – tBu + MeO + 2H]+, 377.2
[M – I – 2tBu + MeO + 3H]+, 321.1 [M – I – 3tBu + MeO +
4H]+.
Iron(III) 1,1,1-Trifluoro-2,4-pentanedioneate (2): 1,1,1-trifluoro-2,4-
pentanedione (10.00 g, 0.0648 mol), iron(III) chloride (3.70 g,
0.0216 mol) and sodium acetate (8.80 g, 0.0648 mol) were dissolved
in a 50:50 ethanol/water mixture (50 mL). The solution was heated
to 60 °C for 1 h with stirring. A red precipitate formed on cooling
with an ice bath. The solid was collected by filtration and washed
with water (25 mL). Drying the solid in vacuo yielded 2 (10.90 g,
43.9%) as a red powder. The IR spectrum was found to be in excel-
lent agreement with that in the literature.[41] M.p. 110–114 °C.
Scheme 6. NMR spectroscopic numbering scheme for O=PI(O-2,4-
tBu2C6H3)2.
O=PI(OPh)2: This is a modified version of entry 1 in Table 4.
Phosphorus triiodide (5.68 g, 13.9 mmol), phenol (2.60 g,
27.6 mmol) and toluene (20 mL) were heated to 80 °C with vigor-
ous stirring, and dry air was bubbled through the reaction mixture
at a rate of 40 mL/min. After 5 h the air flow was stopped, and the
reaction mixture was allowed to cool to room temperature. The
solvent was removed in vacuo to yield O=PI(OPh)2 (3.8 g, 76%) as
a brown oil, which solidified on prolonged standing at 5 °C. Fur-
ther purification by chromatography was not possible because of
rapid hydrolysis on silica. 31P{1H} NMR (109.4 MHz, CDCl3): δ
Acknowledgments
We thank Thermphos International and the Engineering and Phys-
ical Science Research Council (EPSRC) for support and Willem
Schipper of Thermphos International for his valuable suggestions
throughout this work. We also thank Mrs. Caroline E. R. Hors-
= –47.0 (s) ppm. 1H NMR (270.2 MHz, CDCl3): δ = 6.80–7.51 burgh for measurement of mass spectra and Dr. David T. Richens
(complex multiplet) ppm. 13C{1H} NMR (67.9 MHz, CDCl3): δ =
122.7 (p-C), 127.1 (m-C), 131.8 (o-C), 150.3 (i-C) ppm. IR (KBr
for advice on oxidation catalysis.
disc): ν = 3044 (s, νCH), 1593 (s), 1487 (vs), 1365 (m), 1263 (s,
˜
[1] R. Gächter, H. Müller in Plastics Additives, 2nd Edition,
Hanser Publishers, New York, 1984.
[2] K. Solbu, S. Thorud, M. Hersson, S. Øvrebø, D. G. Ellingsen,
E. Lundanes, P. Molander, J. Chromatogr. A 2007, 1161, 275–
283.
νP=O), 1226 (s), 1179 (s), 1158 (vs), 1071 (m), 1024 (s), 1011 (s),
960 (vs), 782 (s), 510 (s) cm–1. MS (EI+): m/z = 359.9 [M]+, 233.0
[M – I]+, 126.9 [I]+. HRMS (EI+): calcd. for C12H10O3PI 359.9412;
found 359.9421; error 2.4 ppm.
[3] Official Journal of the European Union, L396, Regulation (EC)
No. 1907/2006.
[4] Phosphorus World, Chemistry, Biochemistry & Technology,
D. E. C. Corbridge, Harrogate, UK (published on CD), 2005.
[5] a) M. Peruzzini, Speciality Chemicals Magazine 2003, 23, 32–
35; b) M. Caporali, L. Gonsalvi, A. Rossin, M. Peruzzini,
Chem. Rev. 2010, 110, 4178–4235.
(PhO)2(O)P–O–P(O)(OPh)2: Diphenyl phosphoroiodidate O=PI-
(OPh)2 (0.5 g, 0.0014 mol) and diphenyl phosphate O=POH(OPh)
(0.35 g, 0.0014 mol) were heated at reflux in toluene (10 mL) for
2
2 h. By 31P NMR spectroscopy, the resulting solution was shown
to contain 86% of (PhO)2(O)P–O–P(O)(OPh)2, along with some
unreacted starting materials. The identity of the compound was
confirmed by comparing its 31P NMR shift with the literature
value[39] and by mass spectrometry. MS (ES+): m/z = 504.6 [M +
Na]+.
[6] Ya. Dorfman, M. Aleshkova, G. Polimbetova, L. Levina, T.
Petrova, R. Abdreimova, D. Doroshkevich, Russ. Chem. Rev.
1993, 62, 877–896.
[7] Ya. Dorfman, R. Abdreimova, D. Akbaeva, Kinet. Catal. 1993,
General Procedure for Reactions of O=PI(OPh)2 with Phenol: The
results are shown in Table 5. The reactions were performed in a
100 mL round-bottomed Schlenk flask under nitrogen. PhOH (typ-
ically ca. 1.2 g, 13 mmol), O=PI(OPh)2 (typically ca. 4.7 g,
13 mmol) and toluene (typically 10 mL) were added into the flask,
iron acetylacetonate (0.25 molar equivalents) was also added to the
flask where appropriate. The reaction mixtures were heated to
80 °C with vigorous stirring. The progress of the reactions was
monitored by 31P NMR spectroscopy, and the reactions were con-
tinued until all the starting material was consumed.
34, 103–111.
[8] R. Abdreimova, F. Kh. Faizova, D. Akbayeva, G. Polimbetova,
S. Aibasova, A. Borangazieva, M. Aliev, Eurasian Chem.-Tech-
nol. J. 2002, 4, 11–17.
[9] R. Abdreimova, D. Akbayeva, G. Polimbetova, A. Caminade,
J. Majoral, Phosphorus Sulfur Silicon Relat. Elem. 2000, 156,
239–254.
[10] Yu. Budnikova, Yu. Kargin, B. Martyov, V. Turygin, A. Tomi-
lov, J. Electroanal. Chem. 2001, 507, 157–169.
[11] Yu. Budnikova, D. Yakhvarov, O. J. Sinyashin, J. Organomet.
Chem. 2005, 690, 2416–2425.
2146
www.eurjic.org
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2011, 2138–2147