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ARTICLE
4b: White moist solid (1.88 g, 97%), 1H NMR (200 MHz, CHCl3). White solid (195 mg, 53%), 1H NMR (500 MHz,
DOI: 10.1039/C5RA13912K
DMSO-d6
,
δ
): 1.30 (s, 9H), 6.25 (d, 1H,
J
J
= 2.4 Hz), 6.32 (dd, CDCl3,
= 8.9 Hz), 10.42 (s, 6.68 (s, 1H), 6.97 (s, 1H), 7.16 (t, 1H,
: 195.2 [M+H]+, 217.2
= 7.6 Hz), 7.25 (t, 2H, = 7.3 Hz), 7.44 – 7.49 (m, 3H), 7.83
(dd, 2H, = 8.0 Hz,
= 1.8 Hz), 8.64 (s, 1H), 12.62 (s, 1H). 13
NMR (125 MHz, CDCl3, ): 205.4, 177.3, 166.2, 163.6, 160.5,
(5a) and 1-(3-acetyl-2,4-dihydroxyphenyl)-3-phenylpropan- 140.2, 131.9, 131.3, 130.0, 129.1, 128.7, 128.4, 126.5, 126.3,
δ): 3.04 (t, 2H, J = 7.6 Hz), 3.42 (t, 2H, J = 7.6 Hz),
1H, = 2.4 Hz,
J
J
= 8.9 Hz), 7.80 (d, 1H,
J = 7.3 Hz), 7.20 (d, 2H,
1H), 12.57 (s, 1H). Mass spectrum,
[M+Na]+.
1-(5-Acetyl-2,4-dihydroxyphenyl)-3-phenylpropan-1-one
m
/
z
J
J
J
J
C
δ
1-one (6a). 1-(2,4-Dihydroxyphenyl)-3-phenylpropan-1-one 4a 118.2, 116.6, 107.2, 105.4, 40.2, 29.7. Mass spectrum,
m/z:
(1.97 mg, 8.1 mmol), zinc chloride (1.66 mg, 12.2 mmol), 371.2 [M+H]+, 393.2 [M+Na]+, 409.2 [M+K]+. Anal. Calcd. for
acetic anhydride (1.54 ml, 16.2 mmol) and glacial acetic acid C24H18O4, %: C 77.91; H 4.90. Found, %: C 77.83; H 4.95.
(10 ml) were stirred at 80°C for 1 h under N2, then poured on 7-Methoxy-2-phenyl-6-(3-phenylpropanoyl)-4
H-chromen-4-
ice and extracted with CHCl3, washed with 0.1 M HCl and then one. 1d): 7-hydroxy-2-phenyl-6-(3-phenylpropanoyl)-4H-
(
water, and dried over MgSO4. The obtained mixture of isomers chromen-4-one 1b (185 mg, 0.5 mmol), dimethylsulfate (69
5a and 6a was separated using column chromatography (SiO2, mg, 0.55 mmol), K2CO3 (76 mg, 0.55 mmol) and DMF (1 ml)
CHCl3).
5a: White moist solid (1.17 g, 51%), 1H NMR (200 MHz, collected precipitate was purified with use of flash
DMSO-d6 ): 2.61 (s, 3H), 2.92 (t, 2H, = 7.6 Hz), 3.43 (t, 2H, chromatography (SiO2, 2% i-PrOH in CHCl3). White solid (176
= 7.6 Hz), 6.36 (s, 1H), 7.18 (m, 1H,
= 4.4 Hz), 8.39 (s, 1H), 12.70 (broad s, 2H). Mass spectrum, Hz), 3.22 (t, 2H,
: 285.2 [M+H]+, 307.1 [M+Na]+.
1H), 7.13 (t, 1H,
= 7.3 Hz), 7.44 – 7.50 (m, 3H), 7.83 (dd, 2H,
= 1.7 Hz), 8.42 (s, 1H). 13C NMR (125 MHz, CDCl3,
= 4.4 Hz), 199.8, 177.3, 163.3, 162.3, 159.4, 141.3, 131.7, 131.5, 129.1,
= 9.0 Hz), 12.89 (broad 128.8, 128.4, 127.5, 126.2, 117.4, 107.8, 99.8, 56.4, 45.1, 30.3.
were stirred at RT for 10 h, and then diluted with water. The
,
δ
J
J
1
J
J
m
= 4.4 Hz), 7.25 (d, 4H, mg, 92%), H NMR (500 MHz, CDCl3,
= 7.6 Hz), 3.92 (s, 3H), 6.71 (s, 1H), 6.94 (s,
= 7.3 Hz), 7.16 (d, 2H, = 7.6 Hz), 7.22 (t,
= 7.9 Hz,
):
δ): 2.97 (t, 2H, J = 7.6
J
J
/
z
J
6a: White moist solid (0.18 g, 8%), 1H NMR (200 MHz, 2H,
J
J
DMSO-d6
= 7.5 Hz), 6.47 (d, 1H,
7.27 (d, 4H, = 4.4 Hz), 8.04 (d, 1H,
,
δ
): 2.58 (s, 3H), 2.92 (t, 2H,
J
= 7.5 Hz), 3.30 (t, 2H,
J
δ
J
J
= 9.0 Hz), 7.18 (m, 1H, J
J
J
s, 1H), 14.24 (broad s, 1H). Mass spectrum,
306.8 [M+Na]+, 322.8 [M+K]+.
m/z m/z
: 284.9 [M+H]+, Mass spectrum, : 385.0 [M+H]+, 407.0 [M+Na]+, 422.9
[M+K]+. Anal. Calcd. for C25H20O4, %: C 78.11; H 5.24.
Found, %: C 78.02; H 5.29.
1-(3-Acetyl-2,4-dihydroxyphenyl)-2,2-dimethylpropan-1-
one
phenyl)-2,2-dimethylpropan-1-one (4b) according to the proce- chromen-4-one.
(
6b). The compound was prepared from 1-(2,4-dihydroxy- 3-Hydroxy-7-methoxy-2-phenyl-6-(3-phenylpropanoyl)-4
1c): 7-Methoxy-2-phenyl-6-(3-phenylpropa-
-chromen-4-one (1d) (0.096 g, 0.25 mmol), acetone
): 1.27 (s, 9H), 2.58 (s, 3H), 6.46 (d, (0.25 ml), CHCl3 (2.5 ml) and water (2.5 ml) were cooled to 0 –
= 9.0 Hz), 7.81 (d, 1H,
= 9.0 Hz), 12.16 (broad s, 1H), 5°С. Oxone© (0.3 g) and K2CO3 (0.2 g, 3.6 mmol) were added
14.12 (broad s, 1H). Mass spectrum, in four portions to the vigorously stirred suspension within 50
: 237.2 [M+H]+.
(2 )-1-[2,4-dihydroxy-5-(3-phenylpropanoyl)phenyl]-3-phe- h, the mixture temperature was maintained at ≤ 5°С. The
H-
(
1
dure described for 5a and 6b. White moist solid (6%). H NMR noyl)-4
(200 MHz, DMSO-d6
1H,
H
,
δ
J
J
m/z
E
nylprop-2-en-1-one. (1e): 1-(5-Acetyl-2,4-dihydroxyphenyl)- organic layer was separated, TFA (0.05 ml) was added, and the
3-phenylpropan-1-one 5a (0.284 mg, 1 mmol), benzaldehyde mixture was stirred for 0.5 h at RT. The residue after
(117 mg, 1.1 mmol), KOH (448 mg, 8 mmol) and 80% aqueous evaporation was reprecipitated from DMSO solution by
NMP (2 ml) were stirred for 15 h at RT, neutralized by 0.1 M dropwise addition of MeOH. Pale yellow powder (89 mg,
1
HCl, extracted with CHCl3 and washed 3 times with water. The 89%), H NMR (500 MHz, CDCl3,
δ
): 2.98 (t, 2H,
J = 7.6 Hz),
crude product was purified with use of flash chromatography 3.23 (t, 2H,
(SiO2, CHCl3). Yellow powder (180 mg, 48 %), H NMR (500 = 7.3 Hz), 7.17 (d, 2H,
J
= 7.6 Hz), 3.93 (s, 3H), 6.93 (s, 1H), 7.13 (t, 1H, J
1
J
= 7.5 Hz), 7.22 (t, 2H,
J
= 7.4 Hz),
MHz, CDCl3,
Hz), 6.51 (s, 1H), 7.25 (t, 1H,
Hz), 7.34 (t, 2H,
7.51 (m, 3H), 7.76 – 7.70 (m, 2H), 7.96 (d, 1H,
8.31 (s, 1H), 13.08 (s, 1H), 13.61 (s, 1H). 13C NMR (125 MHz, 44.1, 29.3. Mass spectrum,
CDCl3,
): 203.7, 191.9, 170.0, 169.0, 146.1, 140.5, 134.4, 439.1 [M+K]+. Anal. Calcd. for C25H20O5, %: C 74.98; H 5.03.
134.3, 131.2, 129.1, 128.8, 128.7, 128.5, 126.6, 119.1, 113.8, Found, %: C 75.05; H 5.10.
113.2, 105.3, 39.7, 30.7. Mass spectrum,
: 373.0 [M+H]+, 3,7-Dihydroxy-2-phenyl-6-(3-phenylpropanoyl)-4
394.9 [M+Na]+, 410.9 [M+K]+. Anal. Calcd. for C24H20O4, %: en-4-one.
1a): To a solution of 3-hydroxy-7-methoxy-2-
phenyl-6-(3-phenylpropanoyl)-4 -chromen-4-one 1c (40 mg,
-chromen-4- 0.1 mmol) in CH2Cl2 (1 ml) under N2, BBr3 (125 mg, 0.5
δ
): 3.15 (t, 2H,
J
J
= 7.7 Hz), 3.36 (t, 2H,
= 7.0 Hz), 7.30 (d, 2H,
J
J
= 7.7 7.40 (t, 1H,
J
= 7.4 Hz), 7.46 (t, 2H,
J
= 7.6 Hz), 8.15 (d, 2H,
J
= 7.6 = 7.9 Hz), 8.45 (s, 1H). 13C NMR (125 MHz, CDCl3,
δ): 198.7,
J
= 7.0 Hz), 7.45 (d, 1H,
J
= 15.5 Hz), 7.47 – 171.7, 161.2, 157.5, 143.5, 140.2, 137.3, 129.8, 129.2, 127.8,
= 15.5 Hz), 127.6, 127.5, 127.4, 126.5, 126.4, 125.1, 113.2, 98.6, 55.4,
: 401.2 [M+H]+, 423.2 [M+Na]+,
J
m/z
δ
m
/
z
H-chrom-
(
C 77.40; H 5.41. Found, %: C 77.03; H 5.49.
H
7-Hydroxy-2-phenyl-6-(3-phenylpropanoyl)-4
H
one.
(1b): (2E)-1-[2,4-dihydroxy-5-(3-phenylpropanoyl)phe- mmol) was added and the mixture was stirred for 2 h. A few
nyl]-3-phenylprop-2-en-1-one 1e (372 mg, 1 mmol), iodine (13 drops of methanol were added, the solution was diluted with
mg, 0.1 mmol) and DMSO (2 ml) were heated at 90°C for 4 h, CH2Cl2 and washed with water. Residue after evaporation was
diluted with thiosulfate aqueous solution, extracted by CHCl3 purified using HPLC with gradient elution (C18, 50 – 80 %
1
and purified by flash chromatography (SiO2, 2% i-PrOH in acetonitrile in water). Pale yellow solid (34 mg, 87%), H NMR
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