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The resulting crude product was filtered, washed with water and
recrystallized in methanol. After drying in vacuo, 4-methylcyclohex-
anone triperoxide (230 mg, 0.60 mmol) was obtained as solid material
in 36% yield. 1H NMR (400 MHz, CDCl3, CHCl3 = 7.26 ppm): δ =
2.29−2.10 (m, 6 H), 1.67−1.09 (m, 21 H), 0.94−0.90 (m, 9 H) ppm.
13C{1H} NMR (101 MHz, CDCl3, CDCl3 = 77.16 ppm): δ = 107.9,
107.8, 107.7, 32.0, 31.9, 31.8, 31.7, 31.3, 31.2, 31.1, 31.1, 31.0, 30.9,
28.8, 28.7, 21.8, 21.7, 21.6 ppm. HRMS (ESI) m/z calcd for
C21H36O6Na [M + Na]+ 407.2410, found: 407.2412. Mp: 104−106
°C.
mmol, 1.0 equiv) and 1,1-dimethoxycyclopentane (620 μL, 4.46
mmol, 1.3 equiv) were dissolved in 3 mL of diethyl ether. Boron
trifluoride etherate (130 μL, 1.03 mmol, 0.3 equiv) was added at 0−5
°C, and the reaction mixture was stirred for 16 h at room temperature.
Then 30 mL of petroleum ether was added, and the mixture was
washed with a 2% sodium hydroxide solution (20 mL), water (2 × 20
mL) at 40 °C, and 50% aqueous methanol at 40 °C and dried over
MgSO4. After filtration, the solvent was evaporated and the crude
product was purified by column chromatography (PE/EE= 50:1).
Heterotrimer 21 (752 mg, 2.29 mmol) was obtained as a solid
1
material in 67% yield. H NMR (400 MHz, CDCl3, CHCl3 = 7.26
1,1′-Dihydroperoxydi(cyclopentyl)peroxide (17). To a mixture of
cyclopentanone (860 μL, 9.70 mmol, 1.0 equiv) and water (1.5 mL)
cooled to 0−5 °C was added a 30% hydrogen peroxide solution (3.0
mL, 29.4 mmol, 3.0 equiv) and concd hydrochloric acid (100 μL, 0.98
mmol, 0.1 equiv). The reaction mixture was stirred for 48 h at room
temperature. The solid was filtered off, washed with distilled water,
and dried under reduced pressure. Product 17 (764 mg, 3.26 mmol)
ppm): δ = 2.24−2.17 (m, 2 H), 1.90−1.40 (m, 26 H) ppm. 13C{1H}
NMR (101 MHz, CDCl3, CDCl3 = 77.16 ppm): δ = 118.8, 108.1,
33.6, 30.8, 25.7, 24.7, 22.9 ppm. HRMS (ESI) m/z calcd for
C17H28O6Na [M + Na]+ 351.1784, found: 351.1798. Mp: 64−65 °C.
7,8,16,7,25,26-Hexaoxatrispiro[5.2.69.2.618.26]hexacosane (22).
1,1′-Dihydroperoxydi(cycloheptyl)peroxide (19) (800 mg, 2.76
mmol, 1.0 equiv) and 1,1-dimethoxycyclohexane(550 μL, 3.59
mmol, 1.3 equiv) were dissolved in 3 mL of diethyl ether. Boron
trifluoride etherate (100 μL, 0.83 mmol, 0.3 equiv) was added, and
the reaction mixture was stirred for 16 h at room temperature. Then
30 mL of petroleum ether was added, and the mixture was washed
with a 2% sodium hydroxide solution (20 mL), water (2 × 20 mL) at
40 °C and 50% aqueous methanol at 40 °C and dried over MgSO4.
The solvent was removed, and the crude product purified by column
chromatography (PE/EE= 90:1). Heterotrimer 22 (360 mg, 0.97
1
was obtained as a colorless solid in 66% yield. H NMR (400 MHz,
CDCl3, CHCl3 = 7.26 ppm): δ = 9.93 (s, 2 H), 2.10−1.95 (m, 8 H),
1.80−1.73 (m, 8 H) ppm. 13C{1H} NMR (101 MHz, CDCl3, CDCl3
= 77.16 ppm): δ = 122.7, 33.5, 24.7 ppm. HRMS (ESI) m/z calcd for
C10H18O6Na [M + Na]+ 257.1001, found: 257.0998. Mp: 63−65 °C.
1,1′-Dihydroperoxydi(cyclohexyl)peroxide (18). A mixture of
cyclohexanone (2.1 mL, 20.3 mmol, 1.0 equiv) and water (2.0 mL)
was added at 5 °C to a mixture of 30% hydrogen peroxide solution
(6.2 mL, 29.4 mmol, 3.0 equiv) and concd sulfuric acid (100 μL, 60.8
mmol, 0.1 equiv). The reaction mixture was stirred for 1 h at a
temperature of 5−10 °C. The solid was filtered off, mixed with
distilled water, a saturated sodium hydrogen carbonate solution, and
again distilled water, and then dried under reduced pressure. Product
18 (880 mg, 3.36 mmol) was obtained as a colorless solid in 33%
yield. 1H NMR (400 MHz, CDCl3, CHCl3 = 7.26 ppm): δ = 7.85 (s,
2 H), 1.85−1.81 (m, 8 H), 1.61−1.55 (m, 8 H), 1.49−1.43 (m, 4 H)
ppm. 13C{1H} NMR (101 MHz, CDCl3, CDCl3 = 77.16 ppm): δ =
110.6, 29.7, 25.5, 22.6 ppm. HRMS (ESI) m/z calcd for C12H22O6Na
[M + Na]+ 285.1314, found: 285.1314. Mp: 73−75 °C.
1
mmol) was obtained as solid material in 35% yield. H NMR (600
MHz, CDCl3, CHCl3 = 7.26 ppm): δ = 2.20−2.12 (m, 4 H), 1.70−
1.41 (m, 30 H) ppm. 13C{1H} NMR (101 MHz, CDCl3, CDCl3 =
77.16 ppm): δ = 112.9, 107.8, 33.0, 32.9, 30.8, 30.2, 25.7, 22.9 ppm.
HRMS (ESI) m/z calcd for C20H34O6Na [M + Na]+ 393.2253, found:
393.2268. Mp: 79−82 °C.
18-Methyl-6,7,13,14,21,22-hexaoxatrispiro[4.2.48.2.515.25] doco-
sane (23). 1,1′-Dihydroperoxydi(cyclopentyl)peroxide (17) (700 mg,
2.98 mmol, 1.0 equiv) and 1,1-dimethoxy-4-methylcyclohexane 16
(680 μL, 3.88 mmol, 1.3 equiv) were dissolved in 3 mL of diethyl
ether. Boron trifluoride etherate (130 μL, 1.03 mmol, 0.3 equiv) was
added, and the reaction mixture was stirred for 16 h at room
temperature. Then 30 mL of petroleum ether was added, and the
mixture was washed with a 2% sodium hydroxide solution (20 mL),
water (2 × 20 mL) at 40 °C, and 50% aqueous methanol at 40 °C and
dried over MgSO4. The solvent was evaporated, and the crude
product purified by column chromatography (PE/EE = 50:1).
Heterotrimer 23 (752 mg, 2.29 mmol) was obtained as a colorless
oil in 64% yield. 1H NMR (400 MHz, CDCl3, CHCl3 = 7.26 ppm): δ
= 2.27−2.15 (m, 4 H), 1.74−1.12 (m, 21 H), 0.94−0.90 (m, 3 H)
ppm. 13C{1H} NMR (101 MHz, CDCl3, CDCl3 = 77.16 ppm): δ =
119.2, 108.4, 33.6, 31.8, 31.2, 30.9, 28.7, 24.7, 21.7 ppm. HRMS (ESI)
m/z calcd for C17H28O6Na [M + Na]+ 351.1784, found: 351.1809.
3-Methyl-7,8,15,16,23,24-hexaoxatrispiro[5.2.59.2.517.26]-
tetracosane (24). 1,1′-Dihydroperoxydi(cyclohexyl)peroxide (18)
(813 mg, 3.10 mmol, 1.0 equiv) and 1,1-dimethoxy-4-methylcyclo-
hexane 16 (700 μL, 4.03 mmol, 1.3 equiv) were dissolved in 3 mL of
diethyl ether. Boron trifluoride etherate (120 μL, 0.92 mmol, 0.3
equiv) was added, and the reaction mixture was stirred for 16 h at
room temperature. Then 30 mL of petroleum ether was added, and
the mixture was washed with a 2% sodium hydroxide solution (20
mL) and water (2 × 20 mL) at 40 °C and 50% aqueous methanol at
40 °C and dried over MgSO4. The solvent was evaporated, and the
crude product purified by column chromatography (PE/EE = 90:1).
Heterotrimer 24 (734 mg, 2.06 mmol) was obtained as colorless oil in
1,1ˈ-Dihydroperoxydi(cycloheptyl)peroxide (19). Cycloheptanone
(1.2 mL, 10 mmol, 1.0 equiv) was added to a mixture of 30%
hydrogen peroxide solution (3.2 mL, 31.0 mmol, 3.0 equiv) and
concd hydrochloric acid (720 μL, 7.99 mmol, 0.8 equiv) at a
temperature of −8 °C. The reaction mixture was then stirred for 2 h
at room temperature. The precipitate was filtered off, washed with
distilled water, and dried under reduced pressure. A colorless solid
1
was obtained as product 19 (990 mg, 3.10 mmol) in 68% yield. H
NMR (400 MHz, CDCl3, CHCl3 = 7.26 ppm): δ = 9.62 (s, 2 H),
2.00−1.98 (m, 8 H), 1.64−1.56 (m, 16 H) ppm. 13C{1H} NMR (101
MHz, CDCl3, CDCl3 = 77.16 ppm): δ = 116.4, 33.1, 30.0, 22.9 ppm.
HRMS (ESI) m/z calcd for C14H26O6Na [M + Na]+ 313.1627, found:
313.1627. Mp: 69−72 °C.
Synthesis of Mixed Triperoxides 20−25. 6,7,13,14,21,22-
Hexaoxatrispiro[4.2.48 .2.51 5 .25 ]docosane (20). 1,1′-
Dihydroperoxydi(cyclopentyl)peroxide (17) (560 mg, 2.39 mmol,
1.0 equiv) and 1,1-dimethoxycyclohexane (473 μL, 3.10 mmol, 1.3
equiv) were dissolved in 2 mL of diethyl ether. Boron trifluoride
etherate (60 μL, 0.48 mmol, 0.2 equiv) was added at a temperature of
0−5 °C. The reaction mixture was stirred for 16 h at room
temperature, and then 30 mL of petroleum ether was added. The
reaction mixture was washed with a 2% sodium hydroxide solution
(20 mL), water (2 × 20 mL) at 40 °C and 50% aqueous methanol at
40 °C and dried over MgSO4. After filtration, the solvent was
evaporated, and the crude product was purified by column
chromatography (PE/EE = 20:1). Triperoxide 20 (330 mg, 1.05
1
66% yield. H NMR (400 MHz, CDCl3, CHCl3 = 7.26 ppm): δ =
1
mmol) was obtained as solid material in 44% yield. H NMR (400
2.27−2.11 (m, 2 H), 1.91−1.12 (m, 27 H), 0.93−0.90 (m, 3 H) ppm.
MHz, CDCl3, CHCl3 = 7.26 ppm): δ = 2.26−2.16 (m, 4 H), 1.88−
1.40 (m, 22 H) ppm. 13C{1H} NMR (101 MHz, CDCl3, CDCl3 =
77.16 ppm): δ = 119.1, 108.5, 33.5, 30.8, 25.6, 24.7, 22.8 ppm. HRMS
(ESI) m/z calcd for C16H26O6Na [M + Na]+ 337.1627, found:
337.1624. Mp: 63−65 °C.
13C{1H} NMR (101 MHz, CDCl3, CDCl3 = 77.16 ppm) δ = 107.9,
107.8, 31.9, 31.9, 31.3, 31.0, 30.9, 30.8, 30.7, 30.7, 28.7, 25.7, 22.9,
21.7 ppm. HRMS (ESI) m/z calcd for C19H32O6Na [M + Na]+
379.2097, found: 379.2112.
3-Methyl-7,8,16,17,25,26-hexaoxatrispiro[5.2.69.2.618.26] hexa-
cosane (25). 1,1′-Dihydroperoxydi(cycloheptyl)peroxide (19) (580
mg, 2.0 mmol, 1.0 equiv) and 1,1-dimethoxy-4-methylcyclohexane 16
6,7,14,15,22,23-Hexaoxatrispiro[4.2.58.2.516.25]tricosane (21).
1,1′-Dihydroperoxydi(cyclohexyl)peroxide (18) (900 mg, 3.43
F
J. Org. Chem. XXXX, XXX, XXX−XXX