Ozonolyses of 3-benzoyloxy- and 3-trimethylsiloxy-substituted 2- phenylindenes in methanol: Substituent-dependent modes of capture of the carbonyl oxide intermediates by the solvent

Full text of DOI:10.1021/jo982014h

J . Org. Chem. 1999, 64, 2137-2139
2137
Ozon olyses of 3-Ben zoyloxy- a n d
3-Tr im eth ylsiloxy-Su bstitu ted
2-P h en ylin d en es in Meth a n ol:
Su bstitu en t-Dep en d en t Mod es of Ca p tu r e
of th e Ca r bon yl Oxid e In ter m ed ia tes by th e
Solven t
Kevin J . McCullough,*,1a Rika Takeuchi,1b
Araki Masuyama,1b and Masatomo Nojima*,1b
Department of Chemistry, Heriot-Watt University,
Edinburgh EH14 4AS, Scotland, and Department of
Materials Chemistry, Faculty of Engineering,
Osaka University, Suita, Osaka 565, J apan
Received October 6, 1998
F igu r e 1. Crystal structure of compound 6 (ORTEP,10 50%
probability ellipsoids for non-hydrogen atoms).
In tr od u ction
Sch em e 1
Carbonyl oxides, key intermediates in alkene ozonoly-
sis, are efficiently captured by protic, nucleophilic sol-
vents such as methanol.2 Thus, the corresponding meth-
oxyalkyl hydroperoxides and/or the hemiperacetals,
derived from intramolecular cyclization, are usually
obtained from the ozonolyses of cycloalkenes in methanol.
In certain cases, however, intramolecular partial capture
of the carbonyl oxide moiety by the adjacent carbonyl
group occurs much faster than capture by the solvent,
affording the corresponding R-hydroperoxy-R′-methoxy
cyclic ethers instead.3 We now report that, in the ozo-
nolyses of 3-benzoyloxy- and 3-trimethylsiloxy-substitut-
ed 2-phenylindenes (1 and 7) in methanol, differences in
the respective natures of the substituents at the 3-posi-
tion appear to exert a significant influence on the mode
of capture of the carbonyl oxide intermediates.
Resu lts a n d Discu ssion
3-(Benzoyloxy)-2-phenylindene (1) was treated with
ozone (1.5 equiv) in methanol-methylene chloride at -70
°C. After a conventional workup, 1H and 13C NMR
spectral analysis of the crude product mixture suggested
that 1-(benzoyloxy)-1-hydroxy-4-methoxy-4-phenyl-4,5-
dihydro-1H-2,3-benzodioxepin (5) had been formed quan-
titatively (Scheme 1).4 This product was, however, very
labile and decomposed during column chromatography
on silica gel into a complex mixture of products from
which a solid material (47% yield) could be isolated by
crystallization from diethyl ether-hexane. The structure
of this new crystalline compound, as determined by X-ray
crystallographic analysis (Figure 1),5 was shown to be
the novel 4-methoxy-4-phenyl-4,5-dihydro-1H-2,3-benzo-
dioxepin-1-one (6), derived from elimination of benzoic
acid from 5 (Scheme 1). A solution of 5 in CDCl3 also
decomposed to yield a mixture of 6 and benzoic acid with
a half-life of ca. 1 day at room temperature.
(1) (a) Heriot-Watt University. (b) Osaka University.
(2) (a) Criegee, R. Angew. Chem., Int. Ed. Engl. 1975, 11, 745. (b)
Bailey, P. S. Ozonation in Organic Chemistry; Academic Press: New
York, 1978; Vol. 1; 1982; Vol. 2. (c) Bunnelle, W. H. Chem. Rev. 1991,
91, 335. (d) Kuczkowski, R. L. Advances in Oxygenated Processes; Ed.
Baumstark, A. L., Ed.; J AI Press: Greenwich, 1991; Vol. 3. (e)
McCullough, K. J .; Nojima, M. In Organic Peroxides; Ando, W., Ed.,
Wiley: New York, 1992.
(3) A part of recent publications on the mode of capture of carbonyl
oxide by protic solvent. (a) DeNinno, M. P. J . Am. Chem. Soc. 1995,
117, 9927. (b) Teshima, K.; Kawamura, S.; Ushigoe, Y.; Nojima, M.;
MuCullough, K. J . J . Org. Chem. 1995, 60, 4755. (c) Watanabe, M.;
Harada, N. J . Org. Chem. 1995, 60, 7372. (d) Voss, T.; Prinzbach, H.
Tetrahedron Lett. 1994, 35, 1535.
These results imply that under the directing effect of
the benzoyloxy group,6 the primary ozonide 2 undergoes
(5) Crystal data for (6): C16H14O4, M ) 270.27, colorless needles,
monoclinic, space group P21/n (alt. setting No. 14), a 8.6664(11), b
13.791(2), c 11.7236(14) Å, â 101.142(9)°, U 1374.8(3) Å3, Z ) 4, Dc
1.306 g cm-3, F(000) 568, µ (Mo KR) 0.094 mm-1, graphite monochro-
mated Mo KR, λ ) 0.71073 Å, T ) 293 K. Data were collected on a
Siemens P4 diffractometer, and the structure was solved by direct
methods.10 Final discrepancy factors: R ) 0.066 and Rw ) 0.099.
(6) (a) Velluz, L.; Muller, G.; Mathieu, J .; Poittevin, A. Tetrahedron
1960, 9, 145. (b) Griesbaum, K.; Volpp, W.; Huh, T.-S.; J ung, I. C.
Chem. Ber. 1989, 122, 941.
(4) Sugimoto, T.; Nojima, M.; Kusabayashi, S. J . Org. Chem. 1991,
56, 1672.
10.1021/jo982014h CCC: $18.00 © 1999 American Chemical Society
Published on Web 02/19/1999

2138 J . Org. Chem., Vol. 64, No. 6, 1999
Notes
pair 9 (Scheme 2).8 In addition to any solvent effects, the
sterically crowded nature of intermediate 9 should favor
the participation of either of the neighboring ester group
oxygen atoms in an intramolecular nucleophilic attack
on the electrophilic carbon of the solvated carbonyl oxide,
thereby yielding the pivotal intermediates 10a ,b. Sub-
sequent loss of the trimethylsilyl group from 10a ,b would
provide the hydroperoxy lactone 11. Although methanol
was not incorporated into the observed product, its
presence appears to be essential for the formation of 11
because ozonolysis of 7 in an aprotic solvent such as
diethyl ether provided a complex mixture of unidentified
products.
F igu r e 2. Crystal structure of compound 11 (ORTEP,10 50%
probability ellipsoids for non-hydrogen atoms).
Exp er im en ta l Section
Sch em e 2
Gen er a l. 1H and 13C NMR spectra were obtained in CDCl3
with SiMe4 as standard. 3-(Benzoyloxy)-2-phenylindene (1)4 was
prepared by the reported method: white powder; mp 119-120
°C (from CH2Cl2-hexane); 1H NMR δ 3.92 (s, 2 H), 7.0-8.3 (m,
14 H); IR 1740, 1255, 1245 cm-1. The ozonolysis procedures have
been previously described.9
Ca u tion . Because organic peroxides are potentially hazard-
ous compounds, they must be handled with due care. Avoid
exposure to strong heat or light, mechanical shock, oxidizable
organic materials, or transition-metal ions. No particular dif-
ficulties were experienced in handling any of the new organic
peroxides synthesized in this work using the reaction scales and
procedures described below, together with the safeguard men-
tioned above.
P r ep a r a tion of 2-P h en yl-3-(tr im eth ylsiloxy)in d en e (7).
2-Phenylindanone (5 g, 24 mmol) in dry THF (100 mL) was
stirred with LDA (from 26 mmol of diisopropylamine and 26
mmol of n-BuLi) in THF (100 mL) at -78 °C for 15 min, and
then a solution of chlorotrimethylsilane (2.87 g, 26 mmol) was
added dropwise. The solution was allowed to warm to room
temperature and stirred for 2.5 h. After evaporation of THF
under reduced pressure, hexane was added to precipitate the
lithium salt. After concentration of the filtrate, the residue was
separated by column chromatography on silica gel. Elution with
ether-hexane (3:97) gave indene 7 (4.2 g, 83%): white powder;
mp 91-92 °C (from ethyl acetate-hexane); 1H NMR δ 0.22 (s, 9
H), 3.69 (s, 2 H), 7.2-7.8 (m, 9 H); 13C NMR δ 0.83, 35.96, 118.37,
121.82, 123.27, 126.09, 126.33, 126.90, 128.23, 136.06, 140.78,
142.86, 149.33. Anal. Calcd for C18H20OSi: C, 77.09; H, 7.19.
Found: C, 76.91; H, 7.21.
cleavage to give exclusively the carbonyl oxide/carbonyl
pair 3, which readily undergoes solvent capture by
methanol yielding the R-methoxyalkyl hydroperoxide 4.
Subsequent intramolecular cyclization of the hydroperoxy
group on to the adjacent benzoyloxycarbonyl group
produces the corresponding hemiperacetal 5 (Scheme 1).
A different type of product was obtained from the
ozonolysis of 2-phenyl-3-(trimethylsiloxy)indene (7) under
Ozon olysis of 3-(Ben zoyloxy)-2-p h en ylin d en e (1) in
MeOH-CH2Cl2. To a solution of indene 1 (320 mg, 1.00 mmol)
in MeOH-CH2Cl2 (15 mL, 1:2, v/v) was passed a slow stream of
ozone (1.5 equiv) at -70 °C. The solvent of the reaction mixture
was remove by evaporation under reduced pressure to yield an
1
similar conditions (Scheme 2). The H NMR spectrum of
1
oily residue that gave H and 13C NMR spectral data consistent
the crude product mixture was not consistent with the
formation of a methanol-derived product. On subsequent
purification by column chromatography on silica gel, a
crystalline compound was isolated in 65% yield and
shown by X-ray analysis to be 3-hydroperoxy-3-phenyl-
3,4-dihydro-1H-2-benzopyran-1-one (11) (Figure 2).7
From the structure of the product 11, the direction of
cleavage of the primary ozonide 8 must also be highly
selective, yielding exclusively the carbonyl oxide/carbonyl
with 1-(benzoyloxy)-1-hydroxy-4-methoxy-4-phenyl-4,5-dihydro-
1H-2,3-benzodioxepin (5): 1H NMR δ 3.30 (s, 1 H), 3.35 (s, 1 H),
3.42 (s, 3 H), 4.40 (br s, 1 H, H-D exchange in D2O), 6.7-8.2
(m, 14 H); 13C NMR δ 36.66, 49.97, 108.19, 118.26, 125.66,
125.91, 126.36, 126.73, 127.28, 127.49, 127.84, 129.43, 133.68,
134.75, 135.49, 139.73, 169.85.
Alternatively, the reaction mixture was poured into ice-cold
aqueous NaHCO3 and extracted with ether. After the combined
organic extratcs were dried (anhydrous MgSO4) and concen-
trated under reduced pressure, the residue was crystallized from
ether-hexane to give 4-Methoxy-4-phenyl-4,5-dihydro-1H-2,3-
benzodioxepin-1-one (6) (130 mg, 47%): white powder; mp 91-
93 °C (from ether-hexane); 1H NMR δ 3.08 (d, J ) 14 Hz, 1 H),
3.38 (s, 3 H), 3.68 (d, J ) 14 Hz, 1 H), 6.7-8.2 (m, 9 H); 13C
NMR δ 45.73, 51.18, 109.79, 126.17, 128.00, 128.34, 128.43,
(7) Crystal data for (11): C15H12O4, M ) 256.25, colorless needles,
monoclinic, space group P21/n (alt. setting No. 14), a 7.4180(10), b
10.9760(10), c 14.844(3) Å, â 95.930(10)°, U 1202.1(3) Å3, Z ) 4, Dc
1.416 g cm-3, F(000) 536, µ (Mo KR) 0.103 mm-1, graphite monochro-
mated Mo KR λ ) 0.71073 Å, T ) 160 K. Data were collected on a
Siemens P4 diffractometer, and the structure was solved by direct
methods.10 Final discrepancy factors: R ) 0.050 and Rw ) 0.106. The
authors have deposited the atomic coordinates for the crystal structures
of 6 and 11 with the Cambridge Crystallographic Data Centre. The
coordinates can be obtained on request from the Director, the Cam-
bridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2
1EZ, U.K.
(8) Clark, R. D.; Heathcock, C. H. J . Org. Chem. 1976, 41, 1396.
(9) (a) Fukagawa, R.; Nojima, M. J . Chem. Soc., Perkin Trans. 1
1994, 2449. (b) Yamakoshi, H.; Kawamura, S.; Nojima, M.; Mayr, H.;
Baran, J . J . Org. Chem. 1996, 61, 5939.
(10) SHELXTL/PC (Vers 5.03); Sheldrick, G. M.; Siemens Analytical
X-ray Instruments Inc., Madison, WI.

Notes
J . Org. Chem., Vol. 64, No. 6, 1999 2139
128.86, 129.88, 130.15, 130,50, 132.78, 133.78, 172.36; IR 1750,
3400 cm-1. Anal. Calcd for C16H14O4: C, 70.40; H, 5.14. Found:
C, 70.49; H, 5.16.
164.20; IR 1720, 3300 cm-1. Anal. Calcd for C15H12O4: C, 70.31;
H, 4.72. Found: C, 70.09; H, 4.74.
Ozon olysis of 2-P h en yl-3-(tr im eth ylsiloxy)in d en e (7) in
MeOH-Eth er . To a solution of 7 (280 mg, 2.0 mmol) in
methanol-ether (15 mL, 1:2 v/v) 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 extracted with ether.
After the combined organic extracts were dried (anhydrous
MgSO4) and concentrated under reduce pressure, the residue
was separated by column chromatography on silica gel. Elution
with ether-hexane (1:3, v/v) gave 3-Hydroperoxy-3-phenyl-3,4-
dihydro-1H-2-benzopyran-1-one (11) (165 mg, 65%): white
powder; mp 133-135 °C (from ethyl acetate-hexane); 1H NMR
δ 3.50 (d, J ) 17 Hz, 1 H), 3.64 (d, J ) 17 Hz, 1 H), 7.1-8.1 (m,
9 H), 9.20 (br s, 1 H); 13C NMR δ 37.23, 108.99, 123.90, 125.89,
127.55, 127.78, 128.61, 129.31, 130.26, 134.50, 136.24, 137.59,
Ack n ow led gm en t. This work was supported in part
by a Grant-in-Aid for Scientific Research on Priority
Areas (10153238 and 10166211) from the Ministry of
Education, Science, Culture and Sports of J apan. We
thank British Council (Tokyo) for the award of travel
grants to K.J .McC. and M.N.
Su p p or tin g In for m a tion Ava ila ble: Tables of data de-
rived from the X-ray crystallographic analyses of compounds
6 and 11.
J O982014H