Ozonolyses of 1-Alkyl-Substituted 3-Methylindenes
J . Org. Chem., Vol. 63, No. 16, 1998 5621
molecular weight (vapor-pressure osmometry; CH2Cl2) 684.98.
Anal. Calcd for (C13H16O3)n: C, 70.89; H, 7.32. Found: C,
69.82; H, 6.87. Treatment of either 2b or 3b with 1 equiv of
triphenylphosphine in benzene gave the corresponding keto
aldehyde 15b quantitatively.
chromatography on silica gel (elution with ether-hexane 7:93)
to give phenylcyclopentene ozonide (13b):18 oil; 1H NMR δ 1.8-
2.4 (m, 6 H), 6.0 (s, 1 H), 7.3-7.6 (m, 5 H); 13C NMR δ 15.92,
28.84, 32.94, 103.50, 107.80, 125.64, 128.19, 129.25, 135.72.
Subsequent elution with ether-hexane (7:3) gave hemiperac-
etal 12b (116 mg, 25%). Elution with ether-hexane (1:1) gave
hydroperoxide 14b (155 mg, 35%).
3-Meth oxy-3-ph en yl-7-h ydr oxy-1,2-dioxepan e (12b): oil,
a mixture of two isomers; 1H NMR δ 1.5-2.4 (m, 6 H), 3.14 (s,
1.8 H) + 3.20 (s, 1.2 H), 3.70 (d, J ) 5.0 Hz, 0.4 H, H-D
exchange in D2O) + 4.03 (d, J ) 5.6 Hz, 0.6 H, H-D exchange
in D2O), 5.46 (q, J ) 5.6 Hz, 0.6 H, triplet in D2O), 5.58 (ddd,
J ) 3.0, 5.0, 6.3 Hz, 0.4 H, d × d in D2O), 7.3-7.5 (m, 5 H);
13C NMR δ 17.15, 17.18, 36.50, 36.88, 40.47, 42.21, 49.94,
50.46, 101.19, 103.30, 108.41, 109.24, 125.86, 126.54, 128.23,
128.36, 138.51, 139.55. Anal. Calcd for C12H16O4: C, 64.27;
H, 7.19. Found: C, 64.37; H, 7.48.
exo-1-Isop r op yl-5-m eth yl-4,5-d ih yd r o-1,4-ep oxy-1H-2,3-
ben zodioxepin (1-m eth yl-3-isopr opylin den e ozon ide, exo-
1
2b): mp 78-79 °C (from methanol); H NMR δ 1.15 (d, J )
6.9 Hz, 3 H), 1.22 (d, J ) 6.6 Hz, 3 H), 1.35 (d, J ) 7.3 Hz, 3
H), 2.8-2.9 (m, 1 H), 2.96 (q, J ) 7.3 Hz, 1 H), 5.78 (s, 1 H),
7.2-7.3 (m, 4 H); 13C NMR δ 15.17, 18.28, 19.07, 26.97, 39.19,
105.23, 107.87, 123.34, 126.38, 128.86, 129.00, 133.68, 137.18.
Anal. Calcd for C13H16O3: C, 70.89; H, 7.32. Found: C, 71.28;
H, 7.52.
en d o-2b (in admixture with 60% of exo-2b; characteristic
signals in NMR spectra are shown): oil; 1H NMR δ 1.13 (d, J
) 6.9 Hz, 3 H), 1.21 (d, J ) 6.6 Hz, 3 H), 1.35 (d, J ) 7.3 Hz,
3 H), 2.8-2.9 (m, 1 H), 3.34 (qd, J ) 7.3, 2.0 Hz, 1 H), 5.77 (d,
J ) 2.0 Hz 1 H), 7.2-7.4 (m, 4 H); 13C NMR δ 14.74, 15.22,
19.01, 27.32, 38.17, 104.22, 108.19.
exo-1-ter t-Bu t yl-5-m et h yl-4,5-Dih yd r o-1,4-ep oxy-1H -
2,3-ben zod ioxep in (exo-2d ): mp 119-120 °C; 1H NMR δ
1.19 (d, J ) 7.3 Hz, 3 H), 1.27 (s, 9 H), 2.83 (q, J ) 7.3 Hz, 1
H), 5.64 (s, 1 H), 7.0-7.2 (m, 3 H), 7.58 (d, J ) 7.9 Hz, 1 H);
13C NMR δ 18.60, 27.14, 36.50, 39.23, 105.82, 108.84, 124.76,
125.55, 128.45, 129.31, 134.32, 138.13. Anal. Calcd for
5-Hyd r oxy-5-m eth oxyva ler op h en on e (14b): oil; 1H NMR
δ 1.7-1.9 (m, 4 H), 3.02 (t, J ) 6.9 Hz, 2 H), 3.52 (s, 3 H), 4.79
(t, J ) 5.3 Hz, 1 H), 7.4-8.0 (m, 5 H), 9.64 (br s, 1 H); 13C
NMR δ 19.01, 30.64, 37.77, 55.85, 108.86, 125.86, 126.49,
128.03, 133.12, 136.75, 200.27. Anal. Calcd for C12H16O4: C,
64.27; H, 7.19. Found: C, 64.03; H, 7.23.
1
1-ter t-Bu tylcyclop en ten e ozon id e (13c): oil; H NMR δ
1.03 (s, 9 H), 1.7-2.3 (m, 6 H), 5.76 (s, 1 H); 13C NMR δ 16.09,
25.12, 27.12, 29.42, 36.19, 103.15, 112.35. Anal. Calcd for
C9H16O3: C, 62.77; H, 9.36. Found: C, 62.72; H, 9.15.
C
14H18O3: C, 71.77; H, 7.74. Found: C, 71.81; H, 7.86.
en d o-2d (in admixture with 60% of exo-2d ): oil; 1H NMR δ
ter t-Bu tyl 4-h ydr oper oxy-4-m eth oxybu tyl keton e (14c):
1.23 (d, J ) 7.3 Hz, 3 H), 1.27 (s, 9 H), 3.22 (qd, J ) 7.3 and
1.0 Hz, 1 H), 5.66 (d, J ) 1.0 Hz, 1 H), 7.0-7.6 (m, 4 H); 13C
NMR (only characteristic signals are shown) δ 15.10, 26.96,
36.79, 38.26, 104.28, 109.15.
1
oil; H NMR δ 1.14 (s, 9 H), 1.6-1.7 (m, 4 H), 2.5-2.6 (m, 2
H), 3.50 (s, 3 H), 4.72 (t, J ) 4.9 Hz, 1 H), 8.81 (s,1 H); 13C
NMR δ 18.60, 26.38, 30.59, 35.74, 44.08, 55.80, 108.23, 216.37.
Anal. Calcd for C10H20O4: C, 58.80; H, 9.87. Found: C, 59.01;
H, 9.66.
1
Oligom er 3a : viscous oil; H NMR δ 1.0-2.0 (br s), 2.8-
3.1 (br s), 5.3-5.7 (br s), 6.9-7.8 (br s), the ratio of the peak
areas being 6:1:1:4; IR 1720 (weak), 1120, 1180, 960 cm-1
;
ter t-Bu t yl 5-h yd r op er oxy-5-m et h oxyp en t yl k et on e
(14d ): oil; 1H NMR δ 1.13 (s, 9 H), 1.3-1.8 (m, 6 H), 2.51 (t, J
) 7.3 Hz, 2 H), 3.51 (s, 3 H), 4.74 (t, J ) 2.6 Hz, 1 H), 9.25 (br
s, 1 H); 13C NMR δ 23.43, 24.15, 26.29, 31.13, 36.12, 44.05,
55.83, 108.43, 216.40. Anal. Calcd for C11H22O4: C, 60.81;
H, 9.74. Found: C, 61.03; H, 9.87.
molecular weight (vapor-pressure osmometry; CH2Cl2) 828.55.
Anal. Calcd for (C11H12O3)n: C, 68.74; H, 6.29. Found: C,
67.16; H, 6.58.
Ozon olysis of In d en es 1a -d in Eth er in th e P r esen ce
of Tr iflu or oa cetop h en on e. Ozonolysis of 1a is representa-
tive. Over a solution of indene 1a (298 mg, 2.07 mmol) and
trifluoroacetophenone (358 mg, 2.06 mmol) in ether (20 mL)
was passed a slow stream of ozone (1.5 equiv) at -70 °C. Then,
the reaction mixture was poured into ice-cold aqueous NaHCO3
and was extracted with ether. After the mixture was dried
and concentrated, the products were separated by column
chromatography on silica gel (column, 2 × 50 cm; 20 g of silica
gel). Elution with ether-hexane (7:93, v/v) gave 7a (619 mg,
82%).
Ozon olysis of Vin yl Eth er (E)-16 in Eth er . Over a
solution of (E)-16 (105 mg, 0.39 mmol) in ether (15 mL) was
passed a slow stream of ozone (1 equiv) at -70 °C. After
evaporation of the solvent, the crude products were separated
by column chromatography on silica gel. Elution with ether-
hexane (1:20, v/v) gave a 3:2 mixture of exo- and endo-ozonide
2c (52 mg, 52%). The exo/endo ratio was determined by
comparing the peak areas of the two characteristic methine
signals, δ 3.14 (q, J ) 7.3 Hz) and δ 3.53 (qd, J ) 4.9, 2.3 Hz),
in the 1H NMR spectrum. Subsequent elution with ether-
hexane (1:1, v/v) gave oligoozonide 3c (13 mg, 13%).
1-[2-[1-Met h yl-4-p h en yl-4-(t r iflu or om et h yl)-2,3,5-t r i-
oxa n yl]p h en yl]p r op ion a ld eh yd e (7a ): oil (a mixture of two
1
1
isomers); H NMR δ 1.42 (d, J ) 6.6 Hz) + 1.48 (d, J ) 6.9
Oligom er 3c: viscous oil; H NMR δ 1.2-1.4 (br s), 3.0-
Hz) (3 H), 1.74 (s) + 1.75 (s) (3 H), 4.2-4.4 (m, 1 H), 7.0-7.8
(m, 9 H), 9.72 (s) + 9.74 (s) (1 H); 13C NMR δ 15.47, 16.21,
26.49, 26.70, 49.11, 49.38, 103.76 (q, J ) 34 Hz), 104.26 (q, J
) 34 Hz, 1 H), 112.65, 113.05, 119.07 (q, J ) 284 Hz), 123.07
(q, J ) 288 Hz), 200.57, 200.68. Anal. Calcd for C19H17F3O4:
C, 62.30; H, 4.68. Found: C, 62.50; H,4.76.
3.6 (br s), 5.3-5.7 (br s), 6.9-7.8 (br s), the ratio of the peak
areas being 3:1:1:9; IR 3400, 2940, 2870, 1750, 1670, 1460,
1270, 1080, 1030, 760, 710 cm-1; molecular weight (vapor-
pressure osmometry; CH2Cl2) 531.19. Anal. Calcd for
(C16H14O3)n: C, 74.58; H, 5.55. Found: C, 74.68; H, 6.02.
Ozon olysis of Vin yl Eth er (E)-16 in Eth er in th e
P r esen ce of Tr iflu or oa cetop h en on e. Over a solution of
(E)-16 (13 mg, 0.052 mmol) and trifluoroacetophenone (8.9 mg,
0.052 mmol) in ether (20 mL) was passed a slow stream of
ozone (1.5 equiv) at -70 °C. After workup as above, the
products were separated by column chromatography on silica
gel. Elution with ether-hexane (1:20,v/v) gave ozonide 2c (12
mg, 90%; exo/endo ratio ) 7:3).
Ozon olysis of Vin yl Eth er (Z)-16 in Eth er . Over a
solution of (Z)-16 (157 mg, 0.59 mol) in ether (15 mL) was
passed a slow stream of ozone (1 equiv) at -70 °C. After
evaporation of the solvent, the crude products were separated
by column chromatography on silica gel. Elution with ether-
hexane (1:20, v/v) gave ozonide endo-2c (12 mg, 8%). Subse-
1
Ald eh yd e ozon id e 7b: oil (a mixture of two isomers); H
NMR δ 0.78 (d, J ) 6.9 Hz) + 0.79 (d, J ) 6.9 Hz) + 0.84 (d,
J ) 6.9 Hz) (6 H), 1.45 (d, J ) 6.6 Hz) + 1.48 (d, J ) 6.6 Hz)
(3 H), 2.2-2.4 (m, 1 H), 4.2-4.4 (m, 1 H), 7.1-7.7 (m, 4 H),
9.73 (s, 1 H); 13C NMR δ 15.20, 15.44, 16.39, 17.00, 17.11,
17.20, 36.19, 36.61, 49.22, 49.29, 104.33 (q, J ) 30 Hz), 105.23
(q, J ) 30 Hz), 117.16, 117.23, 121.06 (q, J ) 288 z), 121.13 (J
) 288 Hz), 126.61, 126.85, 127.96, 128.30, 129.18, 129.27,
129.38, 130.26, 132.20, 135.76, 136.59, 136.69, 200.97. Anal.
Calcd for C21H21F3O4: C, 63.96; H, 5.37. Found: C, 63.97; H,
5.37.
Ozon olysis of 1-Alk yl-Su bstitu ted Cyclop en ten es 8a -d
in MeOH-Eth er . Ozonolysis of 8b is representative. Over a
solution of 1-phenylcyclopentene (8b) (288 mg, 2.00 mmol) in
MeOH-ether (15 mL, 1:5, v/v) was passed a slow stream of
ozone (1.5 equiv) at -70 °C. After evaporation of the solvent
under vacuum, the crude products were separated by column
(18) Castonguay, J .; Bertrand, M.; Carles, J .; Fliszar, S.; Rousseau,
Y. Can. J . Chem. 1969, 47, 919.