Organic & Biomolecular Chemistry
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acid (conc. H2SO4) (34.50 cm3, 63.54 g, 0.65 mol), 1-tetrade- (conc. H2SO4) (15.70 cm3, 28.84 g, 0.29 mol), 1-icosene
cene (0.10 dm3, 77.10 g, 0.39 mol) and 2,2′-azobis(isobutyroni- (50.00 g, 0.18 mol) and 1,1′-azobis(cyclohexanecarbonitrile)
trile) (AIBN) (total of all portions: 13.84 g, 84.29 mmol) were (VAZO-88) (total of all portions: 11.00 g, 45.02 mmol) were
used. Purification of 17 was carried out according to the pro- used. Purification of 19 was carried out according to the pro-
cedure described above for 13, with the following modifi- cedure described above for 13, with the following modifi-
cations: (a) 1-adamantanamine (64.00 mg, 0.42 mmol) and cations: (a) 1-adamantanamine (50.80 mg, 0.34 mmol) and
crude tetradecylphosphinic acid 19 (108.80 mg, 0.41 mmol) crude icosylphosphinic acid 19 (114.20 mg, 0.33 mmol) were
were used. The white solid obtained was purified by recrystalli- used. The white solid obtained was not recrystallized, but was
zation from tetrahydrofuran–ethyl acetate (THF–EtOAc) to give washed with hot ethyl acetate to give icosylphosphinate ada-
tetradecylphosphinate adamantan-1-yl-ammonium salt (ada- mantan-1-yl-ammonium salt (adamantanamine derivative of
mantanamine derivative of 17) (161.20 mg, 0.39 mmol) as a 19) (0.16 g, 0.31 mmol) as a bright white soft solid. Regener-
bright white powder. Regeneration of the acid afforded the ation of the acid afforded the product 19 as a bright white
product 17 as a bright white powder (95.00 mg); (b) recrystalli- powder (0.11 g); (b) recrystallization of the yellowish solid
zation of the yellowish solid (99.89 g) from hexane afforded the (57.89 g) from hexane afforded the product 19 as a bright
product 17 as a bright white powder (95.80 g). From the two white fine powder (56.10 g). From the two purification
purification methods described, the product 17 was obtained methods described, the product 19 was obtained as a bright
as a bright white powder (95.90 g, 93%). mp 52–53 °C (from white fine powder (56.21 g, 91%). mp 72–73 °C (from hexane).
hexane). HRMS (ESI−): calculated for C14H30O2P [M − H]− HRMS (ESI−): calculated for C20H42O2P [M − H]− requires
requires 261.1989; found: 261.1998. Elem. Anal. (%): calcu- 345.2928; found: 345.2946. Elem. Anal. (%): calculated for
lated for C14H31O2P requires C, 64.09; H, 11.91; P, 11.81%; C20H43O2P requires C, 69.32; H, 12.51; P, 8.94%; found: C,
found: C, 64.31; H, 11.94; P, 11.64%. IR, νmax (ATIR)/cm−1
:
69.36; H, 12.32; P, 9.24%. IR, νmax (ATIR)/cm−1: 2968, 2927,
2954 (w, C–H), 2915 and 2847 (m, C–H), 2590 (br, PO–H), 2361 2873, 1458 and 1371 (m, C–H), 1269 and 1197 (w, C–H), 1154
(w, P–H), 1468 (m, C–H), 1399, 1308, 1285, 1260, 1236 and (w, PvO), 1086 and 1047 (s, P–OH), 945 (w, P–H), 736 (m,
1
1215 (w, C–H), 1154 (m, PvO), 1075 and 1037 (m, P–OH), 975 CH2), 699 (m, P–C). H NMR (500 MHz, CDCl3): δH 10.73 (1H,
1
1
3
and 959 (m, P–H), 720 and 709 (m, CH2). H NMR (400 MHz, br s, OH), 7.1 (1H, dt, JP–H = 540.4 Hz, JH–H = 1.9 Hz, PH),
1
CDCl3): δH 10.37 (1H, br s, OH), 7.1 (1H, dt, JP–H = 540.3 Hz, 1.80–1.73 (2H, m, PCH2), 1.65–1.56 (2H, m, PCH2CH2), 1.41
3JH–H = 1.7 Hz, PH), 1.80–1.72 (2H, m, PCH2), 1.65–1.54 (2H, (2H, quin., J = 7.0 Hz, PCH2CH2CH2), 1.27 (32H, br s, 16 ×
m, PCH2CH2), 1.40 (2H, quin., J = 6.8 Hz, PCH2CH2CH2), 1.26 CH2), 0.90 (3H, t, J = 6.9 Hz, CH3). 13C NMR (125 MHz, CDCl3):
(20H, br s, 10 × CH2), 0.89 (3H, t, J = 7.1 Hz, CH3). 13C NMR δC 31.95, 30.44 (d, 3JC–P = 16.4 Hz, PCH2CH2CH2), 29.72, 29.70,
3
2
(100 MHz, CDCl3): δC 31.95, 30.44 (d, JC–P = 16.0 Hz, 29.68, 29.66, 29.61, 29.38, 29.16, 28.96, 22.71, 20.59 (d, JC–P
=
PCH2CH2CH2), 29.71, 29.69, 29.67, 29.65, 29.61, 29.38, 29.26 3.7 Hz, PCH2CH2CH2), 14.13 (CH3). 31P NMR (162 MHz,
(d, 1JC–P = 93.7 Hz, PCH2), 29.16, 22.71, 20.63 (d, 2JC–P = 2.9 Hz, CDCl3, proton-coupled): δP 38.39 (d quin., JP–H = 539.9 Hz,
1
PCH2CH2CH2), 14.14 (CH3). 31P NMR (162 MHz, CDCl3, 2JP–H = JP–H = 27.4 Hz, CH2CH2PH). MS (ESI−), m/z (rel. inten-
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2
proton-coupled): δP 38.11 (d quin., JP–H = 539.9 Hz, JP–H
=
sity %): 345 (M − H−, 100%).
ICOSYLPHOSPHINATE ADAMANTAN-1-YL-AMMONIUM SALT (ADAMANTANAMINE
3JP–H = 27.4 Hz, CH2CH2PH). MS (ESI−), m/z (rel. intensity %):
261 (M − H−, 100%).
DERIVATIVE OF 19). mp 148–149 °C. Elem. Anal. (%): calculated
TETRADECYLPHOSPHINATE ADAMANTAN-1-YL-AMMONIUM SALT (ADAMANTA- for C30H60NO2P requires C, 72.39; H, 12.15; N, 2.81; P, 6.22%;
NAMINE DERIVATIVE OF 17). mp 152–153 °C (from THF–EtOAc). IR, found: C, 72.27; H, 12.11; N, 2.70; P, 6.40%. IR, νmax (NaCl,
νmax (NaCl, evap. film)/cm−1: 2913 (s, C–H), 2847 (s, C–H), evap. film)/cm−1: 2921 (br, NH3+), 2919 and 2849 (s, C–H),
+
+
2284 and 2249 (m, P–H), 2065 (w, NH3 ), 1639 and 1621 (m, 2286 and 2249 (m, P–H), 1638 (w, NH3+), 1548 (m, NH3 ), 1470
NH3 ), 1547 (m, NH3+), 1471 (m, C–H), 1453 (m, C–H), 1400 (w, and 1457 (m, C–H), 1400 (w, C–H), 1365 (m, C–H), 1350, 1310,
+
C–H), 1367 (m, C–H), 1349 (w, C–H), 1311 (w, C–H), 1281, 1257 1277, 1265, 1250, 1233 and 1216 (w, C–H), 1154 (s, PvO), 1127
and 1234 (w, C–H), 1207 (m, C–H), 1154 (s, PvO), 1127 (m, (w, C–N), 1040 (s, P–O−), 985 (w, P–H), 720 (w, CH2), 690 (w,
1
C–N), 1042 (s, P–O−), 976 (m, P–H), 719 (m, CH2), 690 (m, P–C). H NMR (400 MHz, CDCl3): δH 8.82 (3H, br s, NH3), 7.0
1
1
P–C). H NMR (400 MHz, CDCl3): δH 8.78 (3H, br s, NH3), 7.0 (1H, d, JP–H = 479.5 Hz, PH), 2.04 (3H, br s), 1.88 (6H, br s),
1
(1H, d, JP–H = 478.7 Hz, PH), 2.04 (3H, br s), 1.88 (6H, br s), 1.60 (6H, br s), 1.46 (4H, br s), 1.29 (2H, br s), 1.18 (32H, br s),
1.60 (6H, br s), 1.46 (4H, br s), 1.29 (2H, br s), 1.17 (20H, br s), 0.81 (3H, t, J = 7.1 Hz, CH3). 13C NMR (75 MHz, CDCl3): δC
0.81 (3H, t, J = 7.1 Hz, CH3). 13C NMR (100 MHz, CDCl3): δC 50.48 (CNH3), 40.53, 35.81, 33.23 (d, JC–P = 90.4 Hz, PCH2),
1
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3
50.57 (CNH3), 40.63, 35.79, 33.27 (d, JC–P = 90.8 Hz, PCH2), 31.95, 31.09 (d, JC–P = 15.8 Hz, PCH2CH2CH2), 29.74, 29.69,
31.95, 31.07 (d, JC–P = 16.0 Hz, PCH2CH2CH2), 29.72, 29.69, 29.56, 29.51, 29.39, 29.02, 22.84, 22.71, 14.14 (CH3). 31P NMR
3
29.67, 29.54, 29.49, 29.39, 29.02, 22.88, 22.71, 14.14 (CH3). 31P (162 MHz, CDCl3): δP 25.69 (CH2PH).
NMR (162 MHz, CDCl3): δP 25.47 (CH2PH).
SODIUM HEXADECYLPHOSPHINATE (20). Ethanol (30 cm3) was
ICOSYLPHOSPHINIC ACID (19). The product 19 was prepared cooled to 0 °C under an atmosphere of dry nitrogen with stir-
according to the procedure described above for 15, with the ring, and sodium hydride (0.14 g, 3.62 mmol, 60 wt% in
following modifications: anhydrous sodium hypophosphite mineral oil) was slowly added over 20 minutes. A solution of
(anh. NaH2PO2) (47.04 g, 0.53 mol), concentrated sulfuric acid hexadecylphosphinic acid 11 (1.00 g, 3.44 mmol) in ethanol
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Org. Biomol. Chem., 2013, 11, 119–129 | 125