Molecules 2018, 23, 2199
8 of 12
3.74 (s, CH3, 3H); 13C-NMR (150 MHz, CD3OD)
δ
170.6, 152.9, 150.8, 142.4, 139.8, 114.6, 113.7, 113.4,
104.2, 51.8; HR-MS (ES) calcd. for C10H10O5 (M)−: 209.0450. Found: 209.0447.
3-(40-hydroxy-3-metoxyphenyl)-(E)-propenoic
obtained from 4-hydroxy-3-methoxybenzaldehyde
acid
methyl
(0.65
ester
(14).
14
was
and
mmol,
100
mg)
(methoxycarbonylmethyl)triphenylphosphine (0.98 mmol, 329 mg). Reaction was in water
(4 mL) at 90 ◦C for 0.5 h. The crude product 14 was purified by column chromatography
◦
(EtOAc/hexane, 5:1
→
1:1) to give 99% (134 mg) of 14 as a white solid. mp. 67–69 C (lit. mp.
62–63 ◦C
[16]). H-NMR (500 MHz, CDCl3)
δ
7.63 (d, 1H, CHβ = CHα, J = 16 Hz), 7.08 (d, aromatic, 1H,
1
J = 1.5 Hz), 7.07 (m, aromatic, 1H, J = 1.5 Hz, J = 2 Hz), 7.02 (m, aromatic, 1H, J = 1.5 Hz), 6.27 (d, 1H,
CHβ = CHα, J = 16 Hz), 3.92 (s, CH3, 3H), 3.79 (s, CH3, 3H); 13C-NMR (125 MHz, CDCl3)
δ 167.7,
147.9, 146.7, 144.9, 126.9, 123.0, 115.1, 114.7, 109.3, 55.9, 51.5; HR-MS (ES) calcd. for C11H12O4 (M)−:
207.0657. Found: 207.0654.
0
4-(2 -hydroxyphenyl)-3(E)-buten-2-one (
6
).
6
was obtained from 2-hydroxybenzaldehyde (0.82 mmol,
85
µ
L) and 1-(triphenylphosphoranylidene)-2-propanone (1.23 mmol, 391 mg). Reaction was in
◦
water (4.0 mL) at 90 C for 2.5 h. The crude product
6
was purified by column chromatography
◦
(EtOAc/hexane, 5:1
→
1:1) to give 85% (112 mg) of
6
as a yellow solid. mp. 137–139 C (lit. mp.
139–140 ◦C [25]); NMR consistent with literature data [25]; HR-MS (ES) calcd. for C10H10O2 (M)−:
161.0603. Found: 161.0604.
4-(30-hydroxyphenyl)-3(E)-buten-2-one (15). 15 was obtained from 3-hydroxybenzaldehyde
(0.82 mmol, 100 mg) and 1-(tripheny◦lphosphoranylidene)-2-propanone (1.23 mmol, 391 mg).
Reaction was in water (4.0 mL) at 90 C for 3 h. The crude product was purified by column
chromatography (EtOAc/hexane, 5:1
(lit. mp. 96–97 ◦C 21]). 1H-NMR (500 MHz, CDCl3)
7.28–7.24 (m, aromatic, 1H), 7.10–7.08 (m, aromatic, 2H), 6.94–6.92 (m, aromatic, 1H), 6.71 (d, 1H, CHβ
= CHα, J = 16.0 Hz), 2.40 (s, CH3, 3H); 13C-NMR (125 MHz, CDCl3)
199.7, 156.5, 144.2, 135.7, 130.2,
→
1:1) to give 97% (128 mg) of 15 as a white solid. mp. 94–96 ◦C
7.50 (d, 1H, CHβ = CHα, J = 16.0 Hz),
[
δ
δ
127.1, 121.0, 118.1, 114.6, 27.4; HR-MS (ES) calcd. for C10H10O2 (M)−: 161.0603. Found: 161.0602.
4-(40-hydroxyphenyl)-3(E)-buten-2-one (16). 16 was obtained from 4-hydroxybenzaldehyde
(0.82 mmol, 100 mg) and 1-(tripheny◦lphosphoranylidene)-2-propanone (1.23 mmol, 391 mg).
Reaction was in water (4.0 mL) at 90 C for 2 h. The crude product was purified by column
chromatography (EtOAc/hexane, 5:1
→
1:1) to give 83% (110 mg) of 16 as a white solid. mp.
110–111 ◦C (lit. mp. 111–113 C [38]). 1H-NMR (500 MHz, CDCl3) 7.53 (d, 1H, CHβ = CHα,
J = 16.0 Hz), 7.45–7.43 (m, aromatic, 2H), 6.93–6.90 (m, aromatic, 2H), 6.62 (d, 1H, CHβ = CHα,
◦
δ
J = 16.0 Hz), 2.39 (s, CH3, 3H); 13C-NMR (125 MHz, CDCl3)
δ 200.1, 159.0, 144.8, 130.4, 126.4, 124.3,
116.2, 27.2; HR-MS (ES) calcd. for C10H10O2 (M)−: 161.0603. Found: 161.0609.
4-(20,40-dihydroxyphenyl)-3(E)-buten-2-one (17). 17 was obtained from 2,4-dihydroxybenzaldehyde
(1.44 mmol, 200 mg) and 1-(triphenyl◦phosphoranylidene)-2-propanone (1.88 mmol, 600 mg).
Reaction was in water (10.0 mL) at 90 C for 2 h. The crude product was purified by column
chromatography (EtOAc/hexane, 5:1
→
1:1) to give 78% (200 mg) of 17 as a bright brown solid;
mp. 118–120 C decomp., H-NMR (500 MHz, CD3OD)
7.91 (d, 1H, CHβ = CHα, J = 16.0 Hz),
7.39 (d, aromatic, 1H, J = 8 Hz), 6.71 (d, 1H, CHβ = CHα, J = 16.0 Hz), 6.34–6.32 (m, aromatic, 2H),
2.32 (s, CH3, 3H); 13C-NMR (125 MHz, CD3OD)
202.2, 162.9, 160.4, 142.6, 131.4, 124.1, 114.6, 109.1,
103.4, 26.7; HR-MS (ES) calcd. for C10H10O3 (M)−: 177.0552. Found: 177.0555.
4-(20,30,40-trihydroxyphenyl)-3(E)-buten-2-one
18). 18 was
◦
1
δ
δ
(
obtained
from
2,3,4-trihydroxybenzaldehyde (1.29 mmol, 200 mg) and 1-(triphenylphosphoranylidene)-2-propanone
◦
(1.94 mmol, 620 mg). Reaction was in water (10.0 mL) at 90 C for 0.5 h. The crude product was
purified by column chromatography (EtOAc/hexane, 2:1
→
1:1) to give 70% (175 mg) of 18 as a bright
brown solid; mp. 98–100 C decomp. 1H-NMR (500 MHz, CD3OD) 7.88 (d, 1H, CHβ = CHα,
J = 16.1 Hz), 6.96 (d, aromatic, 1H, J = 8.7 Hz), 6.72 (d, 1H, CHβ = CHα, J = 16.1 Hz), 6.37 (d, aromatic,
1H, J = 8.6 Hz), 2.33 (s, CH3, 3H); 13C-NMR (125 MHz, CD3OD)
202.1, 150.2, 148.5, 142.9, 134.0, 124.5,
121.1, 115.3, 108.7, 26.7; HR-MS (ES) calcd. for C10H10O4 (M)−: 193.0501. Found: 193.0506.
◦
δ
δ