SYNTHESIS, CHARACTERIZATION, AND PHYTOTOXIC AND ANTIFUNGAL ACTIVITIES
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2,2'-[Biphenyl-2,2'-diylbis(oxy)]diacetic acid (2b).
Colorless crystals, yield 90%. H NMR spectrum, δ,
ppm: 4.56 s (4H, PhOCH2), 6.94 d (2H, J = 8.1 Hz,
Ph-H), 7.01 t (2H, J = 7.2 Hz, Ph-H), 7.26 d (4H, J =
7.8 Hz, Ph-H). EIMS: m/z: 302 [M]+.
4,4'-Bis(4-nitrophenoxy)biphenyl (4a). Light yellow
1
crystals, yield 70%. 1H NMR spectrum, δ, ppm: 7.06 d
(4H, J = 9.3 Hz, Ph-H), 7.16 dt (4H, J = 8.6 Hz, Ph-H),
7.62 d (4H, J = 8.7 Hz, Ph-H), 8.21 d (4H, J = 9 Hz,
Ph-H). EIMS: m/z: 428 [M]+.
2,2'-Bis(3-bromopropoxy)biphenyl (2c). Colorless
powder, yield 50%. 1H NMR spectrum, δ, ppm: 2.12 m
(4H, PhOCH2CH2CH2Br), 3.32 t (4H, J = 6.3 Hz,
PhOCH2CH2CH2Br), 4.03 t (4H, J = 5.7 Hz,
PhOCH2CH2CH2Br), 7.05 d.d (4H, J = 15.6, 7.5 Hz,
Ph-H),7.29 d.d (4H, J = 15.6, 7.8 Hz, Ph-H). EIMS:
m/z: 426 [M]+.
4,4'-(Biphenyl-4,4'-diylbisoxy)dianiline (4b). Colorless
powder, yield 63%. 1H NMR spectrum, δ, ppm: 3.56 s
(4H, NHarom), 6.66 d (4H, J = 8.6 Hz, Ph-H), 6.88 d
(4H, J = 8.0 Hz, Harom), 6.95 d (4H, J = 8.6 Hz, Ph-H),
7.43 d (4H, J = 8.7 Hz, Ph-H). EIMS: m/z: 368 [M]+.
4,4'-Bis(3-bromopropoxy)biphenyl (4c). Colorless
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solid, yield 70%. H NMR spectrum, δ, ppm: 2.32 m
7,8-Dihydro-6H-dibenzo(f,h)-1,5-dioxonine (2d).
Colorless powder, yield 60%. H NMR spectrum, δ,
ppm: 1.98 m (2H, PhOCH2CH2CH2OPh), 4.35 t (4H,
J = 5.1 Hz, PhOCH2CH2CH2OPh), 7.11 t (4H, J =
6.6 Hz, Ph-H), 7.32 m (4H, Ph-H). EIMS: m/z: 226 [M]+.
(4H, PhOCH2CH2CH2Br), 3.60 t (4H, PhOCH2CH2·
CH2Br), 4.12 t (4H, -PhOCH2CH2CH2Br), 6.94 d (4H,
J = 6.6 Hz, Ph-H), 7.45 d (4H, J = 6.3 Hz, Ph-H).
EIMS: m/z: 428 [M]+.
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4,4'-Bis(prop-2-ynyloxy)biphenyl (4d). Colorless
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Diethyl-2,2'-(biphenyl-2,2'-diylbis(oxy))diacetate
(2e). Colorless crystals, yield 65%. 1H NMR spectrum,
δ, ppm: 1.22 t (6H, J = 7.2 Hz, COOCH2CH3 ), 4.22 q
(4H, COOCH2CH3), 4.55 s (4H, PhOCH2), 6.85 d (2H,
J = 8.4 Hz, Ph-H), 7.04 t (2H, J = 7.5 Hz, Ph-H), 7.29
ddd (2H, J = 7.5, 7.5, 5.1 Hz, Ph-H). EIMS: m/z: 358
[M]+.
solid, yield 84%. H NMR spectrum, δ, ppm: 2.51 t
(2H, PhOCH2C≡CH). 4.70 d (4H, J = 2.4 Hz,
PhOCH2C≡CH), 7.01 d (4H, J = 8.8 Hz, Ph-H), 7.46 d
(4H, J = 6.6 Hz, Ph-H). EIMS: m/z: 262 [M]+.
Synthesis of biphenyl derivatives based on Fast
Blue B salt. KI mixture (28 g, 0.17 mmol) in 200 mL
of water with Fast Blue B salt (10.00 g, 21.0 mmol)
was stirred at room temperature for 12 h. The
separated crude product was purified by column
chromatography (CH2Cl2 : hexane, 1 : 4) affording
compound 6a. Additionally, fine crystals of 6b and 6c
were also obtained by column chromatography.
Synthesis of biphenyl analogues based on [1,1'-
biphenyl]-4,4'-diol (3). Compound 3 (250 mg,
1.25 mmol) was dissolved in 20 mL of DMF and
mixed with 1.5 g (10.21 mmol) of K2CO3 and 1.40 g
(7.0 mmol) of 4-nitrobromobenzene. The reaction
mixture was stirred at 120°C for 12 h; H2O (50 mL)
was added to quench the reaction. The separated crude
product was purified by column chromatography
(hexane : ethyl acetate, 6 : 4) affording 4a. The
compound 4a (100 mg, 0.233 mmol) was reduced by
stirring in a mixture with 15 mL of HCl and 315 mg
(1.398 mmol) of SnCl2 at 60°C for 3 h. Potassium
carbonate (10 mL, 2 M) was added to quench the
reaction. The isolated compound 4b was purified by
column chromatography (CH2Cl2 : hexane, 3 : 7).
Refluxing of compound 3 (50 mg, 0.25 mmol) with
345 mg (2.5 mmol) of K2CO3 and 0.21 mL (2 mmol) of
dibromopropane in 15 mL of ethanol for 6 h gave the
product 4c. The product was extracted by CH2Cl2
(50 mL) and purified by column chromatography
(CH2Cl2 : hexane, 4 : 6). Compound 4d was obtained
by refluxing a mixture of 100 mg (0.50 mmol) of
compound 3 with K2CO3 (345 mg, 2.5 mmol) and
propargyl bromide (0.2 mL, 2 mmol) in 20 mL of
ethanol for 2 h.
4,4'-Diiodo-3,3'-dimethoxybiphenyl (6a). Yellow
crystals, yield 70%. 1H NMR spectrum, δ, ppm: 3.92 s
(6H, PhOCH3), 6.88 d.d (2H, J = 6, 1.5 Hz, Ph-H),
6.94 d (2H, J = 1.5 Hz, Ph-H), 7.79 d (2H, J = 6 Hz,
Ph-H). EIMS: m/z: 465.6 [M]+.
4-Iodo-3,3'-dimethoxybiphenyl (6b). Colorless
crystals, yield 25%. 1H NMR spectrum, δ, ppm: 3.85 s
(3H, PhOCH3), 3.92 s (3H, PhOCH3), 6.90 m (1H,
Ph-H), 6.92 d.d (1H, J = 3.3, 7.9, Ph-H), 7.00 d (1H,
J = 1.8 Hz, Ph-H), 7.07 t (1H, J = 2.1 Hz, Ph-H), 7.13
d.d (1H, J = 6.6, 1.2 Hz, Ph-H), 7.36 t (1H, J = 8.1 Hz,
Ph-H), 7.8 d (1H, J = 7.9 Hz, Ph-H). EIMS: m/z: 340
[M]+.
3,3'-Dimethoxybiphenyl (6c). Colorless fine crystals,
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yield 20%, H NMR spectrum, δ, ppm: 3.84 s (6H,
PhOCH3), 6.87 d.d (2H, J = 7.8,1.8 Hz, Ph-H), 7.14 m
(4H, Ph-H), 7.34 t (2H, J = 7.8 Hz, Ph-H). EI-MS:
m/z: 214.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 10 2018