Synthesis of -resorcinol-derived phosphonates
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 11, November, 2020
2151
reaction mixture was treated with methanol and the volatiles were
removed in vacuo. The residue was treated with 10 M HCl (1 mL)
in water (5 mL) and stirred at 23 C for 14 h. Water was removed
in vacuo, to give compound 14 as brown viscous oil, yield 0.43 g
(77%). Found (%): C, 41.10; H, 4.31; P, 15.09. C7H9O5P.
Calculated (%): C, 41.19; H, 4.44; P, 15.17. IR, /cm–1: 3274,
1619, 1520, 1460, 1400, 1310, 1211 (P=O), 1166, 1138, 1090,
933, 975, 937, 842, 811, 764, 742, 702, 669, 627, 543, 485, 459.
1H NMR (D2O), : 3.12 (d, 1 H, CH2, J = 20.5 Hz); 6.49—6.39
(m, 2 H, Ar); 7.12—7.07 (m, 1 H, Ar). 13C—{1H} NMR (D2O),
C: 27.4 (d, J = 134.1 Hz); 103.0 (d, J = 2.4 Hz); 107.6 (br.s);
111.1 (d, J = 9.7 Hz); 132.1 (d, J = 5.7 Hz); 154.8 (d, J = 3.4);
155.41 (s). 31P—{1H} NMR (D2O), P: 26.8 (s). MS (ESI), m/z:
205 [M + H]+.
H(4), J = 8.4 Hz, J = 1.5 Hz). 31P—{1H} NMR (CDCl3),
P: 51.3 (s).
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 19-33-50091)
and the Ministry of Science and Higher Education of the
Russian Federation. D. A. Tatarinov and V. F. Mironov
are grateful for the financial support from the government
assignment Federal Research Center "Kazan Scientific
Center of the Russian Academy of Sciences".
References
Diethyl (2-hydroxy-4-methoxybenzyl)phosphonate (15) was
synthesized using the published procedure25 with minor chang-
es. Amount of BBr3 was reduced to 1.05 equiv. Compound 15
was obtained as reddish highly viscous oil, yield 0.57 g (42%),
m.p. 80—83 C. Found (%): C, 52.68; H, 7.03; P, 11.18.
C12H19O5P. Calculated (%): C, 52.55; H, 6.98; P, 11.29 IR,
/cm–1: 3216 (OH), 2960, 2926, 2873, 2854, 2740, 2366, 2306,
1619, 1599, 1521, 1509, 1465, 1445, 1396, 1369, 1320, 1290,
1230 (P=O), 1203, 1164, 1096, 1035, 984, 961, 841, 810, 734,
701, 634, 577, 513, 489, 467, 413. 1H NMR (CDCl3), : 1.21
(t, 6 H, CH3, J = 7.1 Hz); 3.08 (d, 2 H, CH2P, J = 20.6 Hz);
3.71 (s, 3 H, OCH3); 4.04—3.87 (m, 4 H, OCH2); 6.43 (dd, H(5),
1 H, J = 8.4 Hz, J = 2.5 Hz); 6.51 (d, H(3), 1 H, J = 2.5 Hz);
6.97 (dd, H(6), 1 H, J = 8.3 Hz, J = 2.2 Hz); 8.47 (s, 1 H, OH).
13C—{1H} NMR (CDCl3), C: 16.2 (d, CH3, J = 6.1 Hz), 28.3
(d, CH2P, J = 139.9 Hz); 55.24 (s, OCH3); 62.6 (d, OCH2,
J = 6.7 Hz); 103.4 (s, C(4)); 107.0 (s, C(6)); 110.4 (d, C(2),
J = 9.4 Hz); 132.0 (d, C(7), J = 6.6 Hz); 155.7 (d, C(3),
J = 4.6 Hz); 160.1 (s, C(5)). 31P—{1H} NMR (CDCl3), P: 30.8
(s). MS (ESI), m/z: 245 [M – C2H5]+.
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2-Ethoxy-3,3-dimethyl-3H-benzo[d][1,2]oxaphosphole
2-oxide 3 (17a). A mixture of compound 7b (4.17 g, 27 mmol,
1 equiv.), triethyl phosphite (4.78 mL, 4.63 g, 27 mmol) and
o-xylene (50 mL) was refluxed for 48 h. The solvent was distilled
off at normal pressure and the residue was distilled under vacuum
to give product 17a as slightly yellow oil. Yield 4.72 g (76%), b.p.
85—90 C (0.1 Torr). Physicochemical properties of product 17a
26
coincide with those described previously. IR, /cm–1: 3064,
1609, 1588, 1475, 1455, 1268, 1242 (P=O), 1200, 1035, 859.
1H NMR (CDCl3), : 1.35 (t, 3 H, CH2CH3, J = 7.1 Hz); 1.49
(d, 3 H, C(3)H3, J = 2.5 Hz); 1.53 (d, 3 H, C(3´)H3, J = 2.3 Hz);
4.35—4.25 (m, 2 H, OCH2); 6.99 (br.d, 1 H, H(7), J = 8.0 Hz);
7.07 (br.t, 1 H, H(5), J = 7.5 Hz); 7.16 (td, 1 H, H(4), J = 7.6 Hz,
J = 1.4 Hz); 7.21 (td, 1 H, H(6), J = 7.8 Hz, J = 1.6 Hz). 31P—{1H}
NMR (CDCl3), P: 51.0 (s). MS (ESI), m/z: 227 [M + H]+.
2-Ethoxy-6-methoxy-3,3-dimethyl-3H-benzo[d][1,2]oxa-
phosphole 2-oxide (17b). A mixture of alcohol 7d (0.93 g, 5.1 mol),
triethyl phosphite (0.88 mL, 0.85 g, 5.1 mmol), and o-xylene
(30 mL) was refluxed for 48 h. The solvent was distilled off at
normal pressure and the residue was dried in vacuo (0.05 Torr)
at 120 C. Yield 0.91 g (70%), yellowish oil. Physicochemical
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1.49 (d, 3 H, C(3)H3, J = 2.4 Hz); 1.54 (d, 3 H, C(3´)H3,
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1 H, H(5), J = 8.4 Hz, J = 2.5 Hz, J = 0.9 Hz); 7.08 (dd, 1 H,
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