M. Kalek, J. Stawinski / Tetrahedron 65 (2009) 10406–10412
10411
J5–3¼0.9 Hz), 7.59 (1H, d, H-P, JH-P¼569 Hz), 7.58 (1H, ddd, H3,
J3-P¼8.1 Hz, J3–4¼3.5 Hz, J3–5¼0.9 Hz), 7.26 (1H, ddd, H4,
J4–5¼4.6 Hz, J4–3¼3.5 Hz, J4–5¼0.9 Hz). 13C NMR (100 MHz, DMSO-
(d, C10, J¼2.8 Hz), 132.6 (d, J¼9.7 Hz) and 130.5 (d, J¼11.9 Hz) (C4a,
C4b and C8a, C9a),129.4 (C4, C5),127.5 (C2, C7),125.4 (C3, C6),124.8
(d, C1, C8, J¼11.1 Hz), 123.4 (d, C9, J¼123 Hz). 31P NMR (162 MHz,
d6):
d
135.1 (d, C3, J¼12.5 Hz), 135.0 (d, C2, J¼138 Hz), 133.9 (d, C5,
DMSO-d6):
d
13.6 (d, JP-H¼558 Hz). HRMS: m/z 241.0400 ([M-H]–,
J¼6.3 Hz), 128.5 (d, C4, J¼15.7 Hz). 31P NMR (162 MHz, DMSO-d6):
C14H10O2Pꢂ calcd 241.0424). Known compound.39
d
6.2 (d, JP-H¼569 Hz). vmax (KBr): 3681–3224 (br), 3099, 2383,1407,
1185, 1108, 964 cmꢂ1. HRMS: m/z 146.9812 ([M-H]ꢂ, C4H4O2PSꢂ
4.4.18. 2-Tolylphosphinic acid (22). 1H NMR (400 MHz, DMSO-d6):
calcd 146.9675).
d
7.67 (1H, dd, H6, J6-P¼15.7 Hz, J6-5¼7.3 Hz), 7.55 (1H, d, H-P,
JH-P¼546 Hz), 7.48 (1H, t, H4, J4–3/5¼7.5 Hz), 7.37–7.28 (2H, m, H3,
H5), 2.51 (3H, s, CH3). 13C NMR (100 MHz, DMSO-d6):
140.1 (d, C2,
4.4.12. Naphtalene-1-ylphosphinate (16). 1H NMR (400 MHz, DMSO-
d
d6):
d
8.49 (1H, d, H8, J8–7¼8.6 Hz), 8.16 (1H, d, H4, J4–3¼8.5 Hz), 8.04
J¼10.4 Hz), 132.0 (d, C4, J¼2.5 Hz), 131.9 (d, C1, J¼126 Hz), 130.8 (d,
(1H, d, H5, J5–6¼7.8 Hz), 7.96 (1H, dd, H2, J2-P¼18.2 Hz, J2–3¼6.7 Hz),
C3, J¼11.1 Hz) 130.5 (d, C6, J¼13.3 Hz), 125.6 (d, C5, J¼13.6 Hz), 19.5
7.83 (1H, d, H-P, JH-P¼549 Hz), 7.69–7.59 (3H, m, H3, H6, H7).13C NMR
(CH3). 31P NMR (162 MHz, DMSO-d6):
d
17.7 (dd, JP-H¼546 Hz,
(100 MHz, DMSO-d6):
d
133.0 (d, J¼9.4 Hz) and 131.7 (d, J¼10.0 Hz)
JP-6¼15.7 Hz). HRMS: m/z 155.0257 ([M-H]ꢂ, C7H8O2Pꢂ calcd
(C4a, C8a), 132.6 (d, C4, J¼2.8 Hz), 130.4 (d, C2, J¼13.7 Hz), 130.3 (d,
C1, J¼126 Hz), 128.9 (C5), 127.2 and 126.6 (C6, C7), 125.3 (d, C8,
J¼7.3 Hz), 125.0 (d, C3, J¼15.7 Hz). 31P NMR (162 MHz, DMSO-d6):
155.0267). Known compound.24
4.4.19. Diphenylphosphinic acid (23). 1H NMR (400 MHz, DMSO-
d
18.4 (dd, JP-H¼548 Hz, JP-2¼18.2 Hz). HRMS: m/z 191.0265 ([M-H]ꢂ,
d6):
d
7.73 (4H, ddd, H2, H6, J2/6-P¼11.8 Hz, J2/6–3/5¼8.2 Hz,
C10H8O2Pꢂ calcd 191.0267). Known compound.24
J2/6–4¼1.6 Hz), 7.55–7.42 (6H, m, H3, H4, H5). 13C NMR (100 MHz,
DMSO-d6):
d
135.0 (d, C1, J¼135 Hz),131.5 (d, C4, J¼2.4 Hz),130.9 (d,
4.4.13. Phenathrene-9-ylphosphinate (17). 1H NMR (400 MHz,
DMSO-d6):
C2, C6, J¼9.9 Hz), 128.4 (d, C3, C5, J¼12.6 Hz). 31P NMR (162 MHz,
d
8.93 (1H, d, J¼7.6 Hz) and 8.89 (1H, d, J¼8.7 Hz) (H4, H5),
DMSO-d6): d
23.4 (m). HRMS: m/z 217.0402 ([M-H]ꢂ, C12H10O2Pꢂ
8.55 (1H, d, H8, J8–7¼7.7 Hz), 8.38 (1H, d, H10, J10-P¼20.2 Hz), 8.15 (1H,
calcd 217.0424). This compound is commercially available.
d, H1, J1–2¼7.8 Hz), 7.89 (1H, d, H-P, JH-P¼553 Hz), 7.83–7.70 (4H, m,
H2, H3, H6, H7). 13C NMR (100 MHz, DMSO-d6):
d
132.9 (d, C10,
4.4.20. Bis(4-methoxyphenyl)phosphinic acid (24). 1H NMR (400
J¼14.4 Hz),131.2(d, C4a,J¼2.2 Hz),129.9(d,C8a,J¼9.0 Hz),129.8(C1),
129.6 (d, J¼16.8 Hz) and 129.3 (d, J¼10.2 Hz) (C4b, C10a), 129.2 (C7),
129.2(d, C9, Jw125 Hz),127.5,127.4and127.3(C2,C3, C6),126.3(d, C8,
J¼6.6 Hz), 123.7 and 123.0 (C4, C5). 31P NMR (162 MHz, DMSO-d6):
MHz, DMSO-d6):
d
7.61 (4H, wdd, H2, H6, J2/6-P¼11.4 Hz,
J2/6–3/5¼8.7 Hz), 7.00 (4H, wdd, H3, H5, J3/5–2/6¼8.7 Hz,
J3/5-P¼2.5 Hz), 3.77 (6H, s, CH3). 13C NMR (100 MHz, DMSO-d6):
d
161.5 (d, C4, J¼2.9 Hz), 132.7 (d, C2, C6, J¼11.4 Hz), 127.8 (d, C1,
d
19.7 (dd, JP-H¼553 Hz, JP-10¼20.2 Hz). vmax (KBr): 3668–3219 (br),
J¼141 Hz), 113.8 (d, C3, C5, J¼13.6 Hz), 55.2 (CH3). 31P NMR
1619,1448,1073, 998 cmꢂ1. HRMS:m/z241.0401([M-H]ꢂ, C14H10O2Pꢂ
calcd 241.0424).
(162 MHz, DMSO-d6): d
23.9 (m). HRMS: m/z 277.0658 ([M-H]ꢂ,
C14H14O4Pꢂ calcd 277.0635). Known compound.40
4.4.14. 2-Methoxyphenylphosphinic acid (18). 1H NMR (400 MHz,
4.4.21. Naphthalen-2-yl(phenyl)phosphinic acid (25). 1H NMR (400
DMSO-d6):
d
10.1 (b, ‘POH’), 7.62 (1H, ddd, H6, J6-P¼14.3 Hz,
MHz, DMSO-d6):
d
8.41 (1H, d, H1, J1-P¼14.0 Hz), 8.07 (1H, d, H8,
J6–5¼7.3 Hz, J6–4¼1.7 Hz), 7.56 (1H, wt, H4, J4–3/5¼8.0 Hz), 7.50 (1H, d,
J8–7¼8.1 Hz), 7.98 (1H, dd, H4, J4–3¼8.5 Hz, J4–P¼3.1 Hz), 7.94 (1H, d,
H5, J5–6¼7.7 Hz), 7.83–7.70 (3H, m, H3, H20, H60), 7.65–7.55 (2H, m,
H6, H7), 7.54–7.43 (3H, m, H30, H40, H50). 13C NMR (100 MHz, DMSO-
H-P, JH-P¼562 Hz), 7.14–7.03 (2H, m, H3, H5), 3.82 (3H, s, CH3). 13C
NMR (100 MHz, DMSO-d6):
d
160.8 (d, C2, J¼3.8 Hz), 134.2 (d, C4,
J¼1.4 Hz), 131.7 (d, C6, J¼7.4 Hz), 121.2 (d, C1, J¼128 Hz), 120.4 (d, C5,
d6):
d
135.0 (d, C10, J¼134 Hz), 134.0 (d, C4a, J¼2.8 Hz), 132.3 (d, C2,
J¼12.5 Hz), 111.5 (d, C3, J¼6.6 Hz), 55.8 (CH3). 31P NMR (162 MHz,
J¼135 Hz), 132.1 (d, C1, J¼9.5 Hz), 132.0 (d, C8a, J¼13.3 Hz), 131.5 (d,
C40, J¼2.6 Hz), 130.9 (d, C20, C60, J¼10.4 Hz), 128.8 (C8), 128.5 (d, C30,
C50, J¼12.6 Hz), 128.1 (d, C4, J¼12.4 Hz), 128.0 (C6), 127.7 (C5), 126.9
DMSO-d6):
d
11.8 (dd, JP-H¼562 Hz, JP-6¼14.3 Hz). HRMS: m/z 171.0231
([M-H]ꢂ, C7H8O3Pꢂ calcd 171.0217). Known compound.38
(C7), 126.6 (d, C3, J¼10.8 Hz). 31P NMR (162 MHz, DMSO-d6):
d 23.4
4.4.15. 4-(Hydroxyhydrophosphoryl)-3,5-dimethoxybenzoic acid
(m). HRMS: m/z 267.0602 ([M-H]ꢂ, C16H12O2Pꢂ calcd 267.0580).
(19). 1H NMR (400 MHz, DMSO-d6):
d
7.68 (1H, d, H-P, JH-P¼586 Hz),
Known compound.41
7.18 (2H, d, H2, H6, J2/6-P¼4.7), 3.85 (6H, s, CH3). 13C NMR (100 MHz,
DMSO-d6):
d
166.5 (C]O), 161.4 (C3, C5), 136.0 (C1), 114.0 (d, C4,
4.4.22. 4-Fluorophenyl(4-tolyl)phosphinic acid (26). 1H NMR (400
J¼122 Hz),104.8 (d, C2, C6, J¼6.0 Hz), 56.1 (CH3). 31P NMR (162 MHz,
MHz, DMSO-d6):
d
7.77 (2H, ddd, H2, H6, J2/6-P¼11.6 Hz,
J2/6–3/5¼8.8 Hz, J2/6-F¼5.4 Hz), 7.62 (2H, dd, H20, H60, J2 /6 –P¼12.3 Hz,
0
0
DMSO-d6):
d
8.0 (dt, JP-H¼586 Hz, JP-2/6¼4.7 Hz). vmax (KBr): 3668–
1996 (br), 1714, 1693, 1600, 1574, 1460, 1405, 1226, 1127, 991 cmꢂ1
.
J2 /6 –3 /5 ¼8.1 Hz), 7.33–7.25 (4H, m, H3, H5, H3 , H5 ), 2.32 (3H, s,
0
0
0
0
0
0
HRMS: m/z 245.0497 ([M-H]ꢂ, C9H10O6Pꢂ calcd 245.0215).
CH3). 13C NMR (100 MHz, DMSO-d6):
d
164.0 (dd, C4, J4-F¼253 Hz,
J4-F¼3.3 Hz), 141.5 (d, C40, J4 -P¼3.0 Hz), 133.6 (dd, C2, C6, J¼11.7 Hz,
J¼8.8 Hz), w131.7 (dd, C1, J1-P¼141 Hz, J1-F¼2.8 Hz), 131.5 (d, C10,
0
4.4.16. Benzylphosphinic acid (20). 1H NMR (400 MHz, DMSO-d6):
J1 -P¼141 Hz), 131.0 (d, C20, C60, J2 /6 -P¼10.3 Hz), 129.1 (d, C30, C50,
0
0
0
d
7.31 (2H, t, H3, H5, J3/5–2/6¼J3/5–4¼8.3 Hz) 7.23–7.20 (3H, mm, H2,
0
0
H4, H6), 6.92 (1H, d, H-P, JH-P¼531 Hz), 3.09 (2H, d, CH2,
J3 /5 -P¼13.7 Hz), 115.6 (dd, C3, C5, J3/5-F¼21.6 Hz, J3/5-P¼15.0 Hz), 21.1
JCH2-P¼18.9 Hz). 13C NMR (100 MHz, DMSO-d6):
d
131.9 (d, C1,
(CH3). 31P NMR (162 MHz, DMSO-d6):
d 23.0 (m). vmax (KBr):
J¼7.4 Hz), 129.8 (d, C2, C6, J¼6.0 Hz), 128.4 (d, C3, C5, J¼3.3 Hz),
3684–3343 (br), 2962, 1364, 1226, 1201, 1123, 998 cmꢂ1. HRMS: m/z
126.4 (d, C4, J¼3.5 Hz), 37.7 (d, CH2, J¼85 Hz). 31P NMR (162 MHz,
249.0453 ([M-H]ꢂ, C13H11FO2Pꢂ calcd 249.0481).
DMSO-d6):
d
28.3 (dt, JP-H¼531 Hz, JP-CH2¼18.9 Hz). HRMS: m/z
155.0305 ([M-H]ꢂ, C7H8O2Pꢂ calcd 155.0267). Known compound.24
4.4.23. 3,5-Dimethylphenyl(naphthalen-1-yl)phosphinic acid (27). 1H
NMR (400 MHz, DMSO-d6):
d
8.56 (1H, d, H8, J8-P¼8.7 Hz), 8.19 (1H,
4.4.17. Anthracene-9-ylphosphinate (21). 1H NMR (400 MHz,
ddd, H2, J2-P¼15.0 Hz, J2–3¼7.3 Hz, J2–4¼1.4 Hz), 8.01 (1H, wd, H4,
DMSO-d6):
d
9.02 (2H, d, H1, H8, J1/8–2/7¼9.0 Hz), 8.88 (1H, s, H10),
J4–3¼8.3 Hz), 7.85 (1H, dt, H5, J5–6¼7.5 Hz, J5–4¼J5–7¼2.0 Hz), 7.58–
0
0
8.59 (1H, d, H-P, JH-P¼558 Hz), 8.17 (2H, d, H4, H5 J4/5–3/6¼8.4 Hz),
7.45 (3H, m, H3, H6, H7), 7.42 (2H, d, H20, H60, J2 /6 -P¼13.2 Hz), 7.11
7.56 (2H, wt, H2, H7, J2/7–1/8wJ2/7–3/6w8.8 Hz), 7.58 (2H, wt, H3, H6,
(1H, s, H40), 2.28 (6H, s, CH3). 13C NMR (100 MHz, DMSO-d6):
d 137.6
J
3/6–4/5wJ3/6–2/7w8.8 Hz). 13C NMR (100 MHz, DMSO-d6):
d
133.1
(d, C30, C50, J¼14.0 Hz), 135.2 (d, C1, J¼137 Hz), 133.3 (d, C2,