September 2006
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tered off. The filtrate was diluted with water and extracted with ether. The
organic extracts were washed with water and brine, dried and evaporated
under reduced pressure to give a residue, which was purified by silica gel
column chromatography (hexane : AcOEtꢁ10—30 : 1) to give O,Oꢀ-diallyl-
catechols.
oil. H-NMR d: 2.20 (3H, s, CH3), 4.67, 4.69 (each 2H, s, OCH2), 5.00—
5.02 (2H, m, CꢁCH2), 6.63—6.69 (2H, m, aromatic H), 6.77 (1H, d,
Jꢁ8.1 Hz, aromatic H). MS m/z 176 (Mꢂ). HR-MS m/z Calcd for C11H12O2
(Mꢂ): 176.0836. Found: 176.0837.
6-Methoxy-3-methylene-1,5-benzodioxepane (15d) From 3-methoxy-
catechol (3.009 g, 21.5 mmol), 15d (3.422 g, 83%) was obtained as a color-
less oil. H-NMR d: 3.84 (3H, s, OCH3), 4.77, 4.83 (each 2H, s, OCH2),
1,2-Bis(2-propenyloxy)benzene (1) From catechol (1.009 g, 9.17
1
1
mmol), 1 (1.649 g, 95%) was obtained as a colorless oil. H-NMR d: 4.60
(4H, dt, Jꢁ5.3, 1.6 Hz, OCH2), 5.26 (2H, dq, Jꢁ10.5, 1.6 Hz, CꢁCH2), 5.41
(2H, dq, Jꢁ17.2, 1.6 Hz, CꢁCH2), 6.08 (2H, ddq, Jꢁ17.2, 10.5, 5.3 Hz,
CHꢁCH2), 6.90 (4H, s, aromatic H). MS m/z 190 (Mꢂ). HR-MS m/z Calcd
for C12H14O2 (Mꢂ): 190.0993. Found: 190.1001.
5.06 (2H, s, CꢁCH2), 6.54—6.58 (2H, m, aromatic H), 6.83 (1H, t,
Jꢁ7.6 Hz, aromatic H). MS m/z 192 (Mꢂ). HR-MS m/z Calcd for C11H12O3
(Mꢂ): 192.0786. Found: 192.0786.
General Procedure for the Deallylation Reaction of O,Oꢀ-Diallylcate-
chols and 3-Methylene-1,5-benzodioxepanes A mixture of O,Oꢀ-diallyl-
catechol (100 mg) or 3-methylene-1,5-benzodioxepanes (100 mg) with 10%
Pd/C (20 mg) in 10% KOH–MeOH (10 ml) was stirred at ambient tempera-
ture for an appropriate time. After the catalyst was filtered, the filtrate was
concentrated in vacuo. A one-molar aqueous HCl solution was added to the
residue and the mixture was extracted with AcOEt. The organic extracts
were washed with brine and dried. The solvent was evaporated under re-
duced pressure to give a residue, which was purified by silica gel TLC to af-
ford the corresponding phenol.
2,3-Bis(2-propenyloxy)benzene (3) From 2,3-dihydroxynaphthalene
(1.004 g, 6.27 mmol), 3 (1.0502 g, 70%) was obtained as colorless crystals.
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mp 59—60 °C (hexane). H-NMR d: 4.70 (4H, dt, Jꢁ5.3, 1.5 Hz, OCH2),
5.31 (2H, dq, Jꢁ10.6, 1.5 Hz, CꢁCHH), 5.48 (2H, dq, Jꢁ17.2, 1.5 Hz,
CꢁCHH), 6.08—6.21 (2H, ddq, Jꢁ17.2, 10.6, 5.3 Hz, CHꢁCH2), 7.12 (2H,
s, aromatic H), 7.31, 7.65 (each 2H, dd, Jꢁ6.1, 3.3 Hz, aromatic H). MS m/z
240 (Mꢂ). HR-MS m/z Calcd for C16H16O2 (Mꢂ): 240.1150. Found:
240.1141.
1,2-Bis(2-propenyloxy)naphthalene (5) From 1,2-dihydroxynaphtha-
lene (0.499 g, 3.11 mmol), 5 (0.552 g, 74%) was obtained as a colorless oil.
1H-NMR d: 4.68—4.73 (4H, m, OCH2), 5.23—5.31 (2H, m, CꢁCHH),
5.41—5.49 (2H, m, CꢁCHH), 6.06—6.26 (2H, m, CHꢁCH2), 7.26, 7.57
(each 1H, d, Jꢁ9 Hz, aromatic H), 7.36, 7.46 (each 1H, dd, Jꢁ6.8, 1.3 Hz,
aromatic H), 7.75—7.78 (each 1H, m, aromatic H), 8.13—8.17 (each 1H, m,
aromatic H). MS m/z 240 (Mꢂ). HR-MS m/z Calcd for C16H16O2 (Mꢂ):
240.1150. Found: 240.1149.
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2-(2-Propenyloxy)phenol (2) Colorless oil. H-NMR d: 4.61 (2H, dt,
Jꢁ4.9, 1.3 Hz, OCH2), 5.32 (1H, ddd, Jꢁ11.7, 2.3, 1.2 Hz, CꢁCHH), 5.41
(1H, ddd, Jꢁ16.8, 2.6, 1.2 Hz, CꢁCHH), 5.66 (1H, br, OH), 6.07 (1H, ddt,
Jꢁ17.2, 10.5, 5.5 Hz, CHꢁCH2), 6.78—6.97 (4H, m, aromatic H). MS m/z
150 (Mꢂ). HR-MS m/z Calcd for C9H10O2 (Mꢂ) 150.0681. Found: 150.0688.
3-(2-Propenyloxy)naphthalen-2-ol (4) Colorless crystals. mp 39—
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39.5 °C. H-NMR d: 4.71 (2H, ddd, Jꢁ5.5, 1.5, 1.3 Hz, OCH2), 5.36 (1H,
3,4-Bis(2-propenyloxy)benzaldehyde (24) From 3,4-dihydroxybenz-
aldehyde (1.269 g, 9.19 mmol), 24 (2.011 g, 100%) was obtained as a color-
dq, Jꢁ10.5, 1.3 Hz, CꢁCHH), 5.46 (1H, dq, Jꢁ17.2, 1.3 Hz, CꢁCHH),
5.97 (1H, br, OH), 6.12 (1H, ddt, Jꢁ17.2, 10.5, 5.5 Hz, CHꢁCH2), 7.11
(1H, s, aromatic H), 7.28—7.33 (3H, m, aromatic H), 7.63—7.66 (2H, m,
aromatic H). MS m/z 200 (Mꢂ). HR-MS m/z Calcd for C13H12O2 (Mꢂ):
200.0836. Found: 200.0835.
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less oil. H-NMR d: 4.66, 4.70 (each 2H, dt, Jꢁ5.0, 1.5 Hz, OCH2), 5.30,
5.34 (each 1H, dq, Jꢁ8.1, 1.3 Hz, CꢁCHH), 5.45 (2H, dq, Jꢁ18.2, 1.3 Hz,
CꢁCHH), 6.02—6.16 (2H, m, CHꢁCH2), 6.98 (1H, d, Jꢁ7.4 Hz, aromatic
H), 7.41—7.45 (2H, m, aromatic H), 9.83 (1H, s, CHO). MS m/z 218 (Mꢂ).
HR-MS m/z Calcd for C13H14O3 (Mꢂ): 218.0943. Found: 218.0943.
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2-(2-Methyl-2-propenyloxy)phenol (7) Colorless oil. H-NMR d: 1.84
(3H, d, Jꢁ0.6 Hz, CH3), 4.50 (2H, s, OCH2), 5.02 (1H, dd, Jꢁ0.9, 0.6 Hz,
CꢁCHH), 5.08 (1H, dd, Jꢁ0.9, 0.6 Hz, CꢁCHH), 5.67 (1H, s, OH), 6.79—
6.96 (4H, m, aromatic H). MS m/z 164 (Mꢂ). HR-MS m/z Calcd for
C10H12O2 (Mꢂ): 164.0837. Found: 164.0831.
General Procedure for the Preparation of 3-Methylene-1,5-benzodiox-
epanes A mixture of catechol (1 eq), 3-chloro-2-methylpropene (1 eq) and
K2CO3 (2 eq) in 2-butanone and DMF (5 : 2) was heated at 80 °C. After com-
pletion of the reaction, the solid mass was filtered. The filtrate was diluted
with water and extracted with ether. The organic extracts were washed with
water and brine, dried and evaporated under reduced pressure to give a
residue, which was purified by silica gel column chromatography
(hexane : AcOEtꢁ10 : 1) to give 3-methylene-1,5-benzodioxepanes.
3-(2-Methyl-2-propenyloxy)naphthalen-2-ol (10) Colorless crystals.
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mp 39 °C. H-NMR d: 1.87 (3H, s, CH3), 4.62 (2H, s, OCH2), 5.06 (1H, s,
CꢁCHH), 5.14 (1H, s, CꢁCHH), 5.97 (1H, s, OH), 7.11 (1H, s, aromatic
H), 7.23—7.34 (3H, m, aromatic H), 7.63—7.66 (2H, m, aromatic H). MS
m/z 214 (Mꢂ). HR-MS m/z Calcd for C14H14O2 (M+): 214.0993. Found:
214.0999.
3-Methylene-1,5-benzodioxepane
(6) From
catechol
(0.554 g,
1
5.03 mmol), 6 (0.521 g, 64%) was obtained as a colorless oil. H-NMR d:
4.76 (4H, s, OCH2), 5.06 (2H, s, CꢁCH2), 6.87—6.96 (4H, m, aromatic H).
MS m/z 162 (Mꢂ). HR-MS m/z Calcd for C10H10O2 (Mꢂ): 162.0680. Found:
168.0675.
1-(2-Methyl-2-propenyloxy)naphthalen-2-ol (12) Colorless crystals.
1H-NMR d: 1.94 (3H, s, CH3), 4.43 (2H, s, OCH2), 5.09 (1H, s, CꢁCHH),
5.30 (1H, s, CꢁCHH), 5.84 (1H, s, OH), 7.22 (1H, d, Jꢁ8.8 Hz, aromatic
H), 7.33 (1H, ddd, Jꢁ8.3, 8.1, 1.3 Hz, aromatic H), 7.47 (1H, ddd, Jꢁ8.4,
8.3, 1.3 Hz, aromatic H), 7.55 (1H, d, Jꢁ8.8 Hz, aromatic H), 7.77 (1H, d,
Jꢁ8.3 Hz, aromatic H), 7.94 (1H, d, Jꢁ8.4 Hz, aromatic H). MS m/z 214
(Mꢂ). HR-MS m/z Calcd for C14H14O2 (Mꢂ): 214.0993. Found: 214.0990.
2-(2-Methyl-2-propenyloxy)-4-nitrophenol (16a) Yellow crystals. mp
3,4-Dihydro-3-methylene-2H-naphtho[2,3-b][1,4]dioxepin (9) From
2,3-dihydroxynaphthalene (1.014 g, 6.33 mmol), 8 (0.701 g, 52%) was ob-
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tained as colorless crystals. mp 77—78 °C (hexane). H-NMR d: 4.79 (4H,
t, Jꢁ1.1 Hz, OCH2), 5.11 (2H, t, Jꢁ1.1 Hz, CꢁCH2), 7.32, 7.65 (each 2H,
dd, Jꢁ6.2, 3.3 Hz, aromatic H), 7.37 (2H, s, aromatic H). MS m/z 212 (Mꢂ).
HR-MS m/z Calcd for C14H12O2 (Mꢂ): 212.0837. Found: 212.0832.
3,4-Dihydro-3-methylene-2H-naphtho[1,2-b][1,4]dioxepin (11) From
1,2-dihydroxynaphthalene (0.500 g, 3.13 mmol), 11 (0.367 g, 55%) was ob-
tained as colorless crystals. 1H-NMR d: 4.90, 4.97 (each 2H, s, OCH2), 5.12
(2H, t, Jꢁ1.1 Hz, CꢁCH2), 7.12 (1H, d, Jꢁ8.8 Hz, aromatic H), 7.34—7.48
(3H, m, aromatic H), 7.73, 8.15 (each 1H, dd, Jꢁ8.3, 0.6 Hz, aromatic H).
MS m/z 212 (Mꢂ). HR-MS m/z Calcd for C14H12O2 (Mꢂ): 212.0837. Found:
212.0831.
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170—171 °C (MeOH–iPr2O). H-NMR d: 1.85 (3H, s, CH3), 4.61 (2H, s,
OCH2), 5.09 (1H, d, Jꢁ1.0 Hz, CꢁCHH), 5.12 (1H, d, Jꢁ1.0 Hz, CꢁCHH),
6.24 (1H, s, OH), 7.00 (1H, d, Jꢁ8.8 Hz, aromatic H), 7.76 (1H, d,
Jꢁ2.6 Hz, aromatic H), 7.88 (1H, dd, Jꢁ8.8, 2.6 Hz, aromatic H). MS m/z
209 (Mꢂ). HR-MS m/z Calcd for C10H12O4N (Mꢂ): 209.0688. Found:
209.0695.
4-Hydroxy-3-(2-methyl-2-propenyloxy)benzaldehyde (16b) Colorless
oil. 1H-NMR d: 1.85 (3H, d, Jꢁ0.6 Hz, CH3), 4.59 (2H, s, OCH2), 5.06 (1H,
dd, Jꢁ0.9, 0.6 Hz, CꢁCHH), 5.10 (1H, dd, Jꢁ0.9, 0.6 Hz, CꢁCHH), 6.28
(1H, s, OH), 7.06, 7.42 (each 1H, d, Jꢁ7.7 Hz, aromatic H), 7.44 (1H, dd,
Jꢁ1.7, 0.7 Hz, aromatic H), 9.81 (1H, d, Jꢁ0.7 Hz, CHO). MS m/z 192
(Mꢂ). HR-MS m/z Calcd for C11H12O3 (Mꢂ): 192.0786. Found: 192.0790.
4-Methyl-2-(2-methyl-2-propenyloxy)phenol (16c) and 5-Methyl-2-(2-
methyl-2-propenyloxy)phenol (17c) An inseparable mixture of 16c and
17c (93%) was obtained as a colorless oil. The ratio of 16c and 17c was de-
3-Methylene-7-nitro-1,5-benzodioxepane (15a) From 4-nitrocatechol
(3.011 g, 19.4 mmol), 15a (3.521 g, 86%) was obtained as yellow crystals.
mp 87—88 °C (2-propanol). 1H-NMR d: 4.83, 4.89 (each 2H, s, OCH2),
5.15, 5.17 (each 1H, s, CꢁCH2), 6.99—7.00 (1H, m, aromatic H), 7.80—
7.85 (2H, m, aromatic H). MS m/z 207 (Mꢂ). HR-MS m/z Calcd for
C10H9O4N (Mꢂ): 207.0531. Found: 207.0534.
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3-Methylene-1,5-benzodioxepane-7-carbaldehyde (15b) From 3,4-di-
hydroxybenzaldehyde (0.996 g, 7.21 mmol), 15b (0.8331 g, 61%) was ob-
termined to be ca. 1 : 2 by H-NMR analysis. H-NMR d: 1.82, 1.83 (to-
gether 3H, each s, CH3), 2.35, 2.27 (together 3H, each s, aromatic CH3),
4.44, 4.45 (together 2H, each s, OCH2), 5.00 (1H, s, ꢁCH2), 5.07 (1H, s,
ꢁCH2), 5.50 (0.66H, s, OH), 5.62 (0.34H, s, OH), 6.59—6.83 (3H, m, aro-
matic H). MS m/z 178 (Mꢂ). HR-MS m/z Calcd for C11H14O2 (Mꢂ):
178.0994. Found: 178.0990.
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tained as a colorless oil. H-NMR d: 4.79, 4.86 (each 2H, s, OCH2), 5.09,
5.13 (each 1H, s, CꢁCH2), 7.01 (1H, d, Jꢁ8.8 Hz, aromatic H), 7.45—7.47
(2H, m, aromatic H), 9.82 (1H, s, CHO). MS m/z 190 (Mꢂ). HR-MS (EI)
m/z Calcd for C11H10O3 (Mꢂ) 190.0629. Found: 190.0629.
7-Methyl-3-methylene-1,5-benzodioxepane (15c) From 4-methylcate-
chol (1.007 g, 8.12 mmol), 15c (0.872 g, 61%) was obtained as a colorless
3-Methoxy-2-(2-methyl-2-propenyloxy)phenol (16d) Colorless oil.
1H-NMR d: 1.87 (3H, s, CH3), 3.85 (3H, s, OCH3), 4.47 (2H, s, OCH2), 4.99