Photochemical vinylcyclopropane rearrangements of 1-substituted-3-(2,2- diphenylvinyl)-2,2-dimethylcyclopropanes to cyclopentenes and different heterocycles

Full text of DOI:10.1021/jo981965s

1056
J . Org. Chem. 1999, 64, 1056-1060
enable studies to be carried out under both direct, using
P h otoch em ica l Vin ylcyclop r op a n e
Rea r r a n gem en ts of
1-Su bstitu ted -3-(2,2-d ip h en ylvin yl)-2,2-
d im eth ylcyclop r op a n es to Cyclop en ten es
a n d Differ en t Heter ocycles
Pyrex glass filtered-light (λ > 300 nm), and triplet-
sensitized photoreaction conditions, employing sensitizers
such as acetophenone or m-methoxyacetophenone.3 The
results of this investigation show that in most cases
substituted vinylcyclopropanes 3 undergo cis-trans
isomerization and rearrangement to cyclopentenes, which
is the normal photochemical reactivity reported previ-
ously for this class of compounds. However, novel pho-
torearrangements to produce 1,2-oxazine and different
furan derivatives, and important differences in reactivity
between the triplet-sensitized and the direct irradiations,
have been observed for the first time in this study.
Diego Armesto,* Maria J . Ortiz, and
Antonia R. Agarrabeitia
Departamento de Quimica Organica I, Facultad de Ciencias
Quimicas, Universidad Complutense, 28040-Madrid, Spain
Received September 29, 1998
In tr od u ction
[1,3]-Sigmatropic rearrangements of vinylcyclopro-
panes have been a subject of interest for many years.1
The results obtained from studies in this area show that
vinylcyclopropanes undergo three types of reorganization
reactions under thermal and photochemical conditions
including cis-trans isomerization, ring opening to pen-
tadienes, and ring expansion to cyclopentenes.1 A major-
ity of past photochemical studies in this area concen-
trated on all-carbon systems. Only a few have focused
on the influence of ring functionality on the photoreac-
tivity of vinylcyclopropanes, and most of these were
related to the photochemistry of pyrethroids.2 The latter
efforts have led to the discovery of a new vinylcyclopro-
pane photorearrangement involving the conversion of (+)-
trans-chrysanthemic acid (1a ) to a racemic mixture of the
four diastereoisomers of 1a and the lactone 2.2b The
formation of 2 suggests the possibility that suitably
substituted vinylcyclopropanes would undergo photore-
arrangements to yield a variety of heterocyclic products.
Resu lts a n d Discu ssion
The vinylcyclopropanes 3 were readily synthesized by
standard procedures starting with ethyl chrysanthemate
(1b). Ozonolysis of 1b yields ethyl 3-formyl-2,2-dimethyl-
1-cyclopropanecarboxylate which is transformed to 3a by
Horner-Emmons olefination with diethyl diphenyl-
methylphosphonate. Hydrolysis of the ester group in 3a
yields the acid 3b. LAH reduction of 3a gives the alcohol
3f which is oxidized to the aldehyde 3c using PCC.
Condensation of 3c with hydroxylamine hydrochloride
affords the oxime 3e. Finally, ketone 3d is obtained by
conversion of 3b into the corresponding acid chloride
followed by reaction with Me2CuLi. All of the substrates
3a -f were obtained as a 1:2 mixture of cis:trans isomers.
Tr ip let-Sen sitized Ir r a d ia tion s. The photochemical
behavior of these substances was first investigated by
using triplet-sensitized conditions (m-methoxyacetophe-
none for 3a -d and 3f and acetophenone for 3e). Irradia-
tion of a solution of m-methoxyacetophenone and 3a in
CH2Cl2 followed by column chromatography on silica gel
gave recovered 3a (74%, 1:1 mixture of cis:trans isomers)
and cyclopentene 5a (19%). The structure of 5a was
established by conventional analytical and spectroscopic
methods.
A reasonable pathway explaining both the isomeriza-
tion and bond reorganization processes begins with
triplet state homolytic cleavage yielding the delocalized
biradical 4a . Rotation and recombination in 4a leads to
trans-cis isomerization while alternative radical recom-
bination of 4a provides 5a .
Compound 3b behaves similarly under triplet-sensi-
tized photoreaction conditions affording the cyclopentene
derivative 5b (17%) and recovered starting material
(80%, 1:1 mixture of cis:trans isomers). Ring expansion
to cyclopentene derivatives along with trans-cis isomer-
izations also occur in the triplet reactions of the carbonyl
derivatives 3c and 3d . However, compounds 3c and 3d
also undergo novel rearrangements to produce furan
derivatives 6a and 7, respectively. Thus, aldehyde 3c
This proposal has led to a study aimed at detecting
novel ring-expansion photoreactions related to the con-
version 1a f 2. A family of substances (3) related to 1a
were selected for this effort because diphenyl substitution
at the vinyl unit in 3 should favor the generation of
biradical intermediates 4 resulting from photoinduced
homolytic cleavage of the allylic cyclopropane ring bonds.
Furthermore, this type of substitution pattern should
(1) Goldschmidt, Z.; Crammer, B. Chem. Soc. Rev. 1988, 17, 229,
and references cited herein.
(2) (a) Sasaki, T.; Eguchi, S.; Ohno, M. J . Org. Chem. 1968, 33, 676.
(b) Sasaki, T.; Eguchi, S.; Ohno, M. J . Org. Chem. 1970, 35, 790. (c)
Ueda, K.; Matsui, M. Tetrahedron 1971, 27, 2771. (d) Ruzo, L. O.;
Holmstead, R. L.; Casida, J . E. Tetrahedron Lett. 1976, 35, 3045. (e)
Ruzo, L. O.; Casida, J . E. J . Chem. Soc., Perkin Trans. 1 1980, 728.
(3) Zimmerman, H. E.; Armesto, D.; Amezua, M. G.; Gannett, T.
P.; J ohnson, R. P. J . Am. Chem. Soc. 1979, 101, 6367.
10.1021/jo981965s CCC: $18.00 © 1999 American Chemical Society
Published on Web 01/13/1999

Notes
J . Org. Chem., Vol. 64, No. 3, 1999 1057
Ta ble 1. P r od u ct Distr ibu tion in th e P h otor ea ction s of
affords recovered starting material (46%, 1:1 mixture of
cis:trans isomers), cyclopentene 5c (20%), and dihydro-
furan 6a (31%). The structure of 6a was assigned on the
basis of analytical and spectroscopic data. Similarly,
ketone 3d yields starting material (25%, 1:1 mixture of
cis:trans isomers), cyclopentene 5d (13%), and the tet-
rahydrofuran 7 (13%) as an inseparable mixture of two
diastereoisomers. The identity of 7 was established on
the basis of conventional analytical and spectroscopic
techniques. Of particular value in this respect was the
comparison of the 1H and 13C NMR spectra of compounds
6a and 7 that shows clearly the structural similarities
between these two compounds, namely, the presence of
a diphenylvinyl unit, a dimethyl-substituted quaternary
carbon, and a furan ring.
3a -f
irradn
isolated products
(yield, %)
cis:trans ratio
of recovered 3
substra
condnsb
3a
3a
3b
3b
3c
3c
3d
3d
3e
3e
3f
A
B
A
B
A
B
A
B
C
B
A
B
5a (19), 3a (74)
3a (65), 8 (19)
5b (17), 3b (80)
3b (75), 8 (15)
5c (20), 3c (46), 6a (31)
5c (24), 3c (30)
5d (13), 3d (25), 7 (13)
3d (34), 7 (19)
5e (20), 3e (48)
5e (9), 3e (47), 12 (6)
3f (60)
1:1
1:1
1:1
1:1
1:1
1:2
1:1
1:2
1:2
2:1
1:2
1:6
3f
3f (40), 14 (20)
a
Compounds 3 were obtained and irradiated as a 1:2 mixture
The formation of 6a can be explained by carbon-
oxygen bonding within the delocalized biradical inter-
mediate 4c while 7 most likely arises by nucleophilic
addition of water to the initial photoproduct dihydrofuran
6b.4
b
of cis:trans isomers. Method A: m-methoxyacetophenone sensi-
tized. Method B: direct irradiation. Method C: acetophenone
sensitized.
drofuran derivative 9 followed by addition of water to give
10 and ethanol elimination to afford 8.4 Compound 3b
Oxime 3e was obtained as a mixture of the four
possible diastereoisomers. 1H NMR analysis demon-
strated that the ratio of cis:trans isomers was 1:2 and
that the ratio of (Z:E)-oxime isomers was 1:1 for the cis
isomer and 3:1 for the trans isomer. Triplet-sensitized
(acetophenone) irradiation of this isomeric mixture af-
forded recovered 3e (48%, 1:2 mixture of the cis:trans pair
of (Z)-oxime isomers and cyclopentene 5e (20%). No
products resulting from carbon-nitrogen bonding within
the intermediate biradical 4e were obtained in this case.
To establish the influence of the stabilization of the
biradical intermediates 4, effected by conjugation of the
radical site with the functional groups at position 1 of
the cyclopropane ring, the study was extended to the
alcohol 3f. Irradiation of 3f, under the same conditions
used for compounds 3a -d , yielded a complex mixture of
highly polar compounds that were not identified and 60%
of recovered starting material as an unchanged mixture
of diastereoisomers. This result shows that the stabiliza-
tion of the intermediate biradical 4, by conjugation with
the functional group originally present in position 1 of
the cyclopropane ring, plays an important role in promot-
ing the recombination of the corresponding intermediate
4 to the starting cyclopropane and to the five-membered-
ring carbocyclic or heterocyclic products. The distribution
of photoproducts, their isolated yields, and the ratio of
cis:trans isomers in the recovered starting materials, for
the triplet-sensitized irradiations of compounds 3, are
presented in Table 1.
behaves similarly on direct irradiation yielding the
lactone 8 in 15% yield along with the starting cyclopro-
pane 3b (75%, 1:1 mixture of diastereoisomers). However,
under these conditions, aldehyde 3c does not give the
dihydrofuran 6a observed in the triplet-sensitized ir-
radiation but rather affords cyclopentene 5c (24%) and
the cyclopropane 3c (30%), as an unchanged 1:2 mixture
of diastereoisomers. In contrast, on direct irradiation
ketone 3d does not gives the cyclopentene derivative 5d
observed in the triplet-sensitized reaction but produces
the tetrahydrofuran 7 (19%) and recovered starting
material (34%) as an unchanged mixture of diastereoi-
somers.
It is interesting that neither the aldehyde 3c nor the
ketone 3d undergo trans:cis isomerization upon direct
irradiation. This suggests the possibility of a concerted
pathway for these reactions.
Direct irradiation of the diastereomeric oximes 3e
yields starting material (47%, 2:1 mixture of the cis:trans
pair of (Z)-oxime isomers), the cyclopentene 5e (9%), and
a new substance (6%) that we identified as the 5,6-
dihydro-4H-1,2-oxazine 12.5 The formation of 12 is best
explained by a mechanism involving hydrogen abstrac-
tion in biradical intermediate 4e, via a five-membered
transition state, to produce an iminoxyl radical 11 that
undergoes cyclization by carbon-oxygen bonding to af-
ford 12 (Scheme 1).
Finally, direct irradiation of a 1:2 mixture of cis:trans
isomers of 3f, in which the biradical intermediate 4f is
not stabilized by additional conjugation, gives recovered
3f (40%, 1:6 cis:trans ratio) and the conjugated diene 14
(20%). The identity of 14 was established on the basis of
analytical and spectroscopic data. This result is surpris-
Dir ect Ir r a d ia tion s. The photochemical reactivity of
vinylcyclopropanes 3 was also probed by use of direct
irradiation conditions. Irradiation of 3a by using Pyrex
glass filtered light (λ > 300 nm) affords recovered 3a
(65%) as a 1:1 mixture of stereoisomers and a new
product (19%) that was identified by conventional spec-
troscopic methods as the 2-furanone 8. The formation of
8 is rationalized by carbon-oxygen bonding within the
delocalized biradical intermediate 4a to yield the dihy-
(4) (a) There are precedents of electrophilic additions to the electron-
rich double bond present in dihydrofurans under very mild conditions
(ref 4b). In this instance the addition of water must occur during
isolation. We believe that this takes place during the elimination of
the solvent by rotary evaporation since the 1H NMR spectra of the
oily residue obtained shows the presence of addition product. (b)
Sargent, M. V.; Dean, F. M. In Comprehensive Heterocyclic Chemistry;
Katritzky, A. R., Rees, C. W., Eds.; Pergamon: Oxford, 1984; Vol. 4, p
653.
(5) (a) The identity of 12 was established by comparison of its
spectroscopic data with those reported (ref 5b) for similar 1,2-oxazines
obtained in the DCA-sensitized irradiation of γ,δ-unsaturated oximes.
(b) Armesto, D.; Austin, M. K.; Griffiths, O. J .; Horspool, W. M.;
Carpintero, M. J . Chem. Soc., Chem. Commun. 1996, 2715.

1058 J . Org. Chem., Vol. 64, No. 3, 1999
Notes
Sch em e 1
cyclopropanes 3, especially those resulting from the
competition between alternative cyclization of the inter-
mediate biradicals, it is clear that suitably substituted
vinylcyclopropanes can be used as accessible starting
materials for the synthesis of cyclopentene derivatives
and different types of heterocyclic compounds.6 Further
studies are underway to determine the factors that
control the competition between the alternative reaction
paths as well as the scope of these new photochemical
reactions.
Sch em e 2
Exp er im en ta l Section
Melting points were determined in open capillaries and are
uncorrected. UV/vis spectra were recorded in CH2Cl2 solution.
Column chromatography was performed using silica 60 (40-63
µm) from Merck. Commercially available starting materials and
reagents were purchased from Aldrich. The photolyses were
carried out in a quartz immersion well apparatus with a Pyrex
filter and a 400-W medium-pressure Hg arc lamp. Solutions of
the compounds and the sensitizer (in the sensitized irradiations)
in dry CH2Cl2 (420 mL) were purged for 1 h with argon and
irradiated under a positive pressure of argon. After completion
of the irradiation, the solvent (and acetophenone or m-meth-
oxyacetophenone in sensitized irradiations) was removed under
reduced pressure, and the products were separated by flash
column chromatography on silica gel.
ing because production of 14 formally involves the 1,2-
migration of a CH2OH group. As far as we are aware,
1,2-migrations of alkyl groups have not been reported
previously in the photochemistry of vinylcyclopropanes.
A mechanism involving homolytic bond fission of the
cyclopropyl 2,3-bond to yield the biradical 13 followed by
1,2-migration of the CH2OH group is proposed to account
for this result (Scheme 2). The distribution of photoprod-
ucts, their isolated yields, and the ratio of cis:trans
isomers in the recovered starting materials, for the direct
irradiations of compounds 3, are collected in Table 1.
Eth yl 3-(2,2-Dip h en ylvin yl)-2,2-d im eth yl-1-cyclop r op a n -
eca r boxyla te (3a ). This compound was synthesized in two steps
from ethyl chrysanthemate according to the following proce-
dure: ethyl chrysanthemate (20 g, 0.102 mol) in CH2Cl2 (200
mL) was ozonized at -78 °C over 2 h. The reaction mixture was
then purged with N2, and triphenylphosphine (28 g, 0.107 mol)
in CH2Cl2 (50 mL) was added. The mixture was warmed to room
temperature and concentrated under reduced pressure. Hexane
(100 mL) was added, and the precipitate was removed by
filtration and washed with hexane and ether. The combined
extracts were evaporated, and the crude product was distilled
under reduced pressure yielding ethyl 3-formyl-2,2-dimethyl-1-
cyclopropanecarboxylate (15.5 g, 90%) as a 1:2 mixture of cis:
Con clu sion s
The results of this study indicate that there is a
marked influence of substitution at the 1-position on the
photochemical reactivity of 1-substituted-2-vinylcyclo-
propanes 3. In addition, the nature of the excited state
also plays an important role in the photochemical reac-
tivity of these systems (see Table 1). Thus, the predomi-
nant triplet reactivity of 3a -d is trans-cis isomerization.
However, in the irradiation of 3e, under these conditions,
only isomerization around the C-N double bond is
observed. Triplet-sensitized irradiations of compounds
3a -e also afford the corresponding cyclopentene deriva-
tives 5a -e. In addition to ring expansion to form cyclo-
pentenes, the carbonyl derivatives 3c and 3d also react
to yield furan derivatives 6a and 7, respectively. The
photoreactivity of 3 under direct irradiation conditions
shows important differences with those displayed under
triplet sensitization conditions. Thus, while 3a and 3b
undergo trans-cis isomerization under direct and sen-
sitized conditions, cyclopropanes 3c and 3d do not
isomerize on direct irradiation. Rather, 3c yields the
cyclopentene 5c, exclusively, while 3d rearranges to the
furan 7, only. Compounds 3e and 3f undergo isomeriza-
tion at the cyclopropane ring only on direct irradiation
but not on triplet sensitization. The furanone 8 is
obtained in the direct irradiation of derivatives 3a and
3b while the corresponding cyclopentenes 5a and 5b are
formed in the triplet-sensitized reactions. Cyclopropane
3e affords the cyclopentene derivative 5e exclusively on
sensitized irradiation while a mixture of 5e and the 1,2-
ozaxine 12 is obtained on direct irradiation. Finally, the
cyclization to cyclopentene derivatives and heterocycles,
such as 1,2 oxazines, and different furan derivatives is
favored when the biradical intermediate 4 is stabilized
by conjugation with a substituent at the 1-position. In
the absence of such stabilization, as in 3f, a different
reaction pathway is followed yielding the conjugated
diene 14.
trans isomers: bp 50 °C (0.8 mm); IR (neat) 1730, 1710 cm-1
;
1H NMR (250 MHz) δ 1.20-1.40 (3 s and 1 t, 8 H, cis and trans),
1.50 (s, 1 H, cis), 1.85 (dd, J ) 6.6, 8.7 Hz, 0.33 H, cis), 2.13 (d,
J ) 8.7 Hz, 0.33 H, cis), 2.46 (m, 1.33 H, trans), 4.16 (m, 2 H,
cis and trans), 9.58 (d, J ) 3.6 Hz, 0.66 H, trans), 9.75 (d, J )
6.6 Hz, 0.33 H, cis); 13C NMR (75 MHz) δ 14.3, 15.0 (cis), 20.6
(trans), 21.0 (trans), 28.3 (cis), 29.8 (cis), 33.2 (trans), 34.5
(trans), 36.5 (cis), 40.8 (cis), 42.0 (trans), 61.1, 169.8, 198.8
(trans), 200.8 (cis); MS m/z 171 (M+ + 1, 5), 170 (M+, 4), 141
(15), 107 (6), 51 (100). Anal. Calcd for C9H14O4 (acid): C, 58.1;
H, 7.3. Found: C, 58.34; H, 7.49.7 To a stirred solution of diethyl
diphenylmethylphosphonate8 (13.4 g, 44 mmol) in dry DME (30
mL) under argon and at 0 °C was added n-BuLi (25.5 mL 1.6 M
in hexane). The resulting red solution was stirred for 1 h at 0
°C, and then ethyl 3-formyl-2,2-dimethyl-1-cyclopropanecarboxy-
late (4.7 g, 27 mmol) in DME (20 mL) was added. The reaction
mixture was stirred at 0 °C for 40 min before being quenched
with H2O and extracted with ether. The combined organic
extracts were dried (MgSO4), filtered, and concentrated to
dryness. Flash chromatography using hexane/Et2O (8:2) yielded
3a (8.5 g, 96%) as an oil and as a 1:2 mixture of cis:trans
1
isomers: IR (neat) 1720 cm-1; H NMR (300 MHz) δ 1.14 (s, 1
H, cis), 1.22 (s, 2 H, trans), 1.25 (t, 3 H), 1.27 (s, 2 H, trans),
1.38 (s, 1 H, cis), 1.62 (d, J ) 5.4 Hz, 0.66 H, trans), 1.68 (d, J
) 8.7 Hz, 0.33 H, cis), 1.83 (app t, J ) 9.0 Hz, 0.33 H, cis), 2.10
(dd, J ) 5.4, 8.7 Hz, 0.66 H, trans), 4.10 (m, 2 H), 5.74 (d, J )
8.7 Hz, 0.66 H, trans), 6.50 (d, J ) 9.4 Hz, 0.33 H, cis), 7.21-
7.34 (m, 10 H); 13C NMR (63 MHz) δ 14.5, 15.2 (cis), 20.1 (trans),
22.7 (trans), 28.1 (cis), 28.4 (cis), 29.9 (trans), 32.7 (cis), 34.1
(6) Yields have not been optimized.
(7) This aldehyde undergoes spontaneous oxidation in the presence
of atmospheric oxygen. The combustion analysis quoted herein corre-
sponds to the carboxylic acid resulting from the oxidation of the
aldehyde.
Although it is difficult to explain at this point the
differences observed in the excited-state reactivity of the
(8) Zimmerman, H. E.; Khun, R. T. Tetrahedron 1978, 34, 1775.

Notes
J . Org. Chem., Vol. 64, No. 3, 1999 1059
(cis), 34.6 (trans), 36.1 (trans), 60.1 (cis), 60.4 (trans), 123.9-
144.0, 171.5 (cis) 171.8 (trans); MS m/z 320 (M+, 26), 247 (100),
167 (60), 152 (18); UV (CH2Cl2) λmax 265 nm (ꢀ 167 00 l mol-1
cm-1). Anal. Calcd for C22H24O2: C, 82.5; H, 7.5. Found: C, 82.20;
H, 7.42.
2.15-2.25 (m, 0.66 H, cis and trans of (Z)- and (E)-oxime
isomers), 5.64 (d, J ) 8.7 Hz, 0.17 H, cis of (E)-oxime isomer),
5.70 (d, J ) 9.3 Hz, 0.5 H, trans of (Z)-oxime isomer), 5.77 (d, J
) 9.6 Hz, 0.17 H, cis of (Z)-oxime isomer), 5.78 (d, J ) 9.0 Hz,
0.17 H, trans of (E)-oxime isomer), 6.20 (d, J ) 8.7 Hz, 0.5 H,
trans of (Z)-oxime isomer), 6.58 (d, J ) 9.0 Hz, 0.17 H, cis of
(Z)-oxime isomer), 7.00 (d, J ) 8.3 Hz, 0.17 H, cis of (E)-oxime
isomer), 7.10-7.27 (m, 10.17 H, trans of (E)-oxime isomer), 7.80,
8.00, 8.25, (br s, 1 H, cis and trans of (Z)- and (E)-oxime isomers);
13C NMR (63 MHz) δ 16.8 (trans), 22.3 (trans), 22.4 (cis), 22.5
(cis), 26.2, 26.7 (trans), 27.0, 27.8 (cis), 28.0, 30.2 (cis), 30.9, 32.6
(trans), 33.4, 34.0 (trans), 34.1, 35.7 (cis), 124.2-149.0, 150.0,
151.1, 151.8, 152.5 (cis and trans); MS m/z 291 (M+, 1), 273 (32),
75 (100); UV (CH2Cl2) λmax 299 nm (ꢀ 15 300).
3-(2,2-Dip h en ylvin yl)-2,2-d im eth yl-1-cyclop r op a n eca r -
boxylic Acid (3b). A solution of KOH (1 g, 12.5 mmol) and ethyl
3-(2,2-diphenylvinyl)-2,2-dimethyl-1-cyclopropanecarboxylate (3a)
(1 g, 3.1 mmol) in ethanol absolute (180 mL) was refluxed for
24 h. The solvent was evaporated to dryness, and the crude
product was dissolved in water. The solution was washed with
ether to remove unreacted starting material, and the aqueous
layer was acidified with a 20% HCl solution and extracted with
ether. The organic phases were dried (MgSO4), filtered, and
concentrated to dryness. Flash chromatography of the residue
using hexane/Et2O (7:3) yielded 3b (812 mg, 89%) as an oil and
as a 1:2 mixture of cis:trans isomers: IR (neat) 3100-2900, 1700
cm-1; 1H NMR (250 MHz) δ 1.14 (s, 1 H, cis), 1.24 (s, 2 H, trans),
1.28 (s, 2 H, trans), 1.39 (s, 1 H, cis), 1.63 (d, J ) 5.3 Hz, 0.66 H,
trans), 1.68 (d, J ) 8.7 Hz, 0.33 H, cis), 1.95 (app t, J ) 9.2 Hz,
0.33 H, cis), 2.13 (dd, J ) 8.7, 5.3 Hz, 0.66 H, trans), 5.73 (d, J
) 8.7 Hz, 0.66 H, trans), 6.43 (d, J ) 9.8 Hz, 0.33 H, cis), 7.15-
7.40 (m, 10 H), 10.81 (br s, 1 H, cis and trans); 13C NMR (63
MHz) δ 14.9 (cis), 15.2 (trans), 20.2 (trans), 22.7 (cis), 28.3
(trans), 29.3 (cis), 30.9 (trans), 32.3 (cis), 34.9 (cis), 35.5 (trans),
123.1-144.4, 177.7 (cis), 178.0 (trans); MS m/z 292 (M+, 71), 275
(2), 247 (83), 205 (93), 165 (39), 91 (100); UV (CH2Cl2) λmax 269
nm (ꢀ 3400).
1-Ace t yl-3-(2,2-d ip h e n ylvin yl)-2,2-d im e t h ylcyclop r o-
p a n e (3d ). This compound was synthesized in two steps from
the acid 3b according to the following procedure: the acid 3b
(590 mg, 2.02 mmol) and thionyl chloride (1 mL) were heated
at reflux for 20 min. The residual thionyl chloride was removed
under reduced pressure yielding 3-(2,2-diphenylvinyl)-2,2-di-
methylcyclopropane-1-carbonyl chloride (627 mg, 100%) as an
oil and as a 1:2 mixture of cis:trans isomers, which was used
without further purification: IR (neat) 1785 cm-1; 1H NMR (300
MHz) δ 1.22 (s, 1 H, cis), 1.27 (s, 2 H, trans), 1.37 (s, 2 H, trans),
1.39 (s, 1 H, cis), 2.23-2.37 (m, 2 H, cis and trans), 5.76 (d, J )
8.4 Hz, 0.66 H, trans), 6.20 (d, J ) 8.7 Hz, 0.33 H, cis), 7.20-
7.43 (m, 10 H). To a stirred suspension of CuI (407 mg, 2.42
mmol) in anhydrous Et2O (100 mL) under argon and at -40 °C
was added MeLi (3.3 mL, 1.6 M in ether). The mixture was
stirred for 30 min, and then 3-(2,2-diphenylvinyl)-2,2-dimethyl-
1-cyclopropanecarbonyl chloride (627 mg, 2.02 mmol) in Et2O
(100 mL) was added. The reaction was kept at -40 °C for 30
min, allowed to warm at 0 °C, and stirred for 30 min before being
quenched with a saturated NH4Cl solution and extracted with
ether. The combined organic phases were dried, filtered, and
concentrated to dryness. Flash chromatography of the residue
using hexane/Et2O (95:5) afforded 3d (374 mg, 64%) as a oil and
2-(2,2-Dip h en ylvin yl)-3-(h yd r oxym eth yl)-1,1-d im eth yl-
cyclop r op a n e (3f). To a stirred suspension of LAH (0.74 g, 19
mmol) in Et2O (75 mL) under argon was added a solution of the
ester 3a (7.74 g, 24 mmol) in anhydrous Et2O (25 mL) dropwise.
The mixture was stirred at room temperature for 1 h. The
reaction was quenched with water and filtered. The ether layer
was separated, dried (MgSO4), filtered, and concentrated to
dryness. Flash chromatography of the residue using hexane/Et2O
(9:1) afforded 3f (6.5 g, 97%) as a oil and as a 1:2 mixture of
cis:trans isomers: IR (neat) 3350, 1620 cm-1
;
1H NMR (300
as a 1:2 mixture of cis:trans isomers: IR (neat) 1705, 1680 cm-1
;
MHz) δ 0.90 (m, 0.66 H, trans), 1.10 (s, 1 H, cis), 1.11 (s, 2 H,
trans), 1.19 (s, 1 H, cis), 1.20 (s, 2 H, trans), 1.46 (m, 1.33 H, cis
and trans), 3.46 (m, 1 H), 3.67 (m, 0.66 H), 3.82 (dd, J ) 7.7, 2.2
Hz, 0.33 H), 5.77 (d, J ) 8.8 Hz, 0.66 H, trans), 5.84 (d, J ) 9.8
Hz, 0.33 H, cis), 7.18-7.40 (m, 10 H), (OH signal not observed);
13C NMR (63 MHz) δ 15.9 (cis), 20.9 (trans), 23.2 (trans), 23.4
(cis), 24.4 (trans), 28.5 (cis), 29.0 (cis), 31.3 (trans), 33.3 (cis),
36.6 (trans), 63.2 (trans), 66.0 (cis), 125.4-143.7; MS m/z 278
(M+, 17), 247 (100), 167 (20); UV (CH2Cl2) λmax 266 nm (ꢀ 15 100).
3-(2,2-Dip h en ylvin yl)-2,2-d im eth yl-1-cyclop r op a n eca r -
ba ld eh yd e (3c). The alcohol 3f (6 g, 21 mmol) and PCC (7 g,
32 mmol) were allowed to react in CH2Cl2 (50 mL) at room
temperature for 4 h. The crude reaction mixture was filtered
through silica gel and the solvent evaporated to dryness. Flash
chromatography of the residue using hexane/Et2O (95:5) give
aldehyde 3c (4.1 g, 69%) as an oil and as a 1:2 mixture of cis:
1H NMR (300 MHz) δ 1.15 (s, 2 H, trans), 1.18 (s, 1H, cis), 1.30
(s, 2H, trans), 1.35 (s, 1H, cis), 1.95 (d, J ) 5.7 Hz, 0.66 H, trans),
2.04 (m, 0.66 H, cis), 2.19 (s, 2H, trans), 2.20-2.30 (m, 0.66 H,
trans, with overlapping singlet at 2.28, 1 H, cis), 5.78 (d, J )
8.4 Hz, 0.66 H, trans), 6.50 (m, 0.33 H, cis), 7.18-7.45 (m, 10
H); 13C NMR (63 MHz) δ 14.7 (cis), 19.5 (trans), 22.9 (trans),
28.7 (cis), 31.3 (cis), 32.5 (trans), 33.5 (cis), 33.6 (trans), 36.1
(trans), 37.6 (cis), 40.4 (cis), 44.5 (trans), 123.6-144.3, 205.5
(trans), 206.0 (cis); MS m/z 290 (M+, 2), 247 (100), 167 (19); UV
(CH2Cl2) λmax 227 nm (ꢀ 4200).
m -Meth oxya cetop h en on e-Sen sitized Ir r a d ia tion of 3a .
Compound 3a (400 mg, 1.25 mmol), as a 1:2 mixture of cis:trans
isomers, and m-methoxyacetophenone (600 mg, 4 mmol) were
irradiated for 3 h. Flash chromatography using hexane/Et2O (9:
1) gave 298 mg (74%) of 3a , as a 1:1 mixture of cis:trans isomers,
and 75 mg (19%) of ethyl 2,2-dimethyl-5,5-diphenyl-3-cyclopen-
tene-1-carboxylate (5a ) as a oil. Further elution with Et2O
afforded 12 mg (3%) of highly polar material. Compound 5a : IR
1
trans isomers: IR (neat) 1700, 1660 cm-1; H NMR (300 MHz)
δ 1.16 (s, 1H, cis), 1.28 (s, 2H, trans), 1.31 (s, 2H, trans), 1.47
(s, 1H, cis), 1.82 (m, 1H, cis and trans), 2.15 (app t, J ) 9.0 Hz,
0.33 H, cis), 2.37 (dd, J ) 5.1, 9.0 Hz, 0.66 H, trans), 5.75 (d, J
) 9.0 Hz, 0.66 H, trans), 6.36 (d, J ) 9.6 Hz, 0.33 H, cis), 7.20-
7.50 (m, 10 H), 9.23 (d, J ) 5.6 Hz, 0.66 H, trans), 9.64 (d, J )
5.7 Hz, 0.33 H, cis); 13C NMR (63 MHz) δ 16.0 (cis), 21.3 (trans),
22.5 (trans), 28.5 (cis), 32.1 (cis), 32.2 (trans), 36.4 (trans), 38.2
(cis), 42.8 (cis), 45.9 (trans), 122.5-145.1, 200.2 (trans), 201.3
(cis); MS m/z 276 (M+, 5), 247 (100), 191 (28), 165 (31); UV (CH2-
Cl2) λmax 268 nm (ꢀ 13 600).
3-(2,2-Dip h en ylvin yl)-2,2-d im eth yl-1-cyclop r op a n eca r -
ba ld eh yd e Oxim e (3e). Aldehyde 3c (2.1 g, 7.6 mmol), hy-
droxylamine hydrochloride (0.8 g, 0.01 mol), and pyridine (0.78
g, 0.01 mol) were heated at reflux in ethanol (50 mL) for 1 h.
After conventional workup, column chromatography of the crude
product on silica gel using hexane/Et2O (9:1) gave the oxime 3e
(1.8 g, 83%) as an oil and as a 1:2 mixture of cis:trans isomers.
The cis isomer was obtained as a 1:1 mixture of the (Z:E)-oxime
isomers and the trans isomer as a 3:1 mixture of (Z:E)-oxime
isomers: IR (neat) 3100-2800, 1610 cm-1; 1H NMR (300 ΜΗz)
δ 1.01, 1.02, 1.05, 1.15, 1.16, 1.17, 1.19, 1.32, (8 s, 6 H), 1.50-
1.80 (m, 1.33 H, cis and trans of (Z)- and (E)-oxime isomers),
(neat) 1755 cm-1 1H NMR (300 MHz) δ 1.03 (t, J ) 7.0 Hz, 3
;
H), 1.13 (s, 3 H), 1.23 (s, 3 H), 3.76 (s, 1H), 3.86 (m, 2 H), 5.78
(d, J ) 5.6 Hz, 1 H), 6.18 (d, J ) 5.6 Hz, 1 H), 7.13-7.43 (m, 10
H); 13C NMR δ 14.1, 24.7, 30.2, 48.5, 59.9, 62.7, 64.9, 126.0-
148.6, 171.9; MS m/z 320 (M+, 50), 247 (100), 191 (32).
m -Meth oxya cetop h en on e-Sen sitized Ir r a d ia tion of 3b.
Compound 3b (575 mg, 1.97 mmol), as a mixture 1:2 of cis:trans
isomers, and m-methoxyacetophenone (4.4 g, 29.2 mmol) were
irradiated for 4 h. Flash chromatography using hexane/Et2O (95:
5) gave 96 mg (17%) of 2,2-dimethyl-5,5-diphenyl-3-cyclopentene-
1-carboxylic acid (5b) as a oil and 459 (80%) of 3b, as a 1:1
mixture of cis:trans isomers. Further elution with Et2O afforded
20 mg (3%) of highly polar material. Compound 5b: IR (neat)
3100-2900, 1700 cm-1; 1H NMR (300 MHz) δ 1.15 (s, 3 H), 1.20
(s, 3 H), 3.77 (s, 1 H), 5.78 (d, J ) 5.6 Hz, 1 H), 6.10 (d, J ) 5.6
Hz, 1 H), 7.00-7.50 (m, 10 H) (COOH signal not observed); 13
C
NMR (63 MHz) δ 28.4, 30.0, 48.4, 62.1, 65.0, 123.2-148.2, 177.4;
MS m/z 292 (M+, 20), 275 (10), 247 (100).
m -Metoxya cetop h en on e-Sen sitized Ir r a d ia tion of 3c.
Compound 3c (398 mg, 1.4 mmol), as a 1:2 mixture of cis:trans
isomers, and m-methoxyacetophenone (3 g, 22 mmol) were

1060 J . Org. Chem., Vol. 64, No. 3, 1999
Notes
irradiated for 1 h. Flash chromatography using hexane/Et2O (95:
5) gave 123 mg (31%) of 2-(2,2-diphenylvinyl)-3,3-dimethyl-2,3-
dihydrofuran (6a ), 80 mg (20%) of 2,2-dimethyl-5,5-diphenyl-3-
cyclopentene-1-carbaldehyde (5c), and 184 mg (46%) of 3c as a
1:1 mixture of cis:trans isomers. Compound 6a : IR (neat) 1610
Dir ect Ir r a d ia tion of 3a . Compound 3a (308 mg, 0.9 mmol)
as a 1:2 mixture of cis:trans isomers was irradiated for 8 h. Flash
chromatography using hexane/Et2O (9:1) gave 201 mg (65%) of
the ester 3a , as a 1:1 mixture of cis:trans isomers, and 60 mg
(19%) of 5-(2,2-diphenylvinyl)-4,4-dimethyltetrahydro-2-furanone
(8). Further elution with Et2O afforded 35 mg (11%) of highly
polar material. Compound 8: IR (neat) 1775 cm-1; 1H NMR (300
MHz) δ 1.02 (s, 3 H), 1.19 (s, 3H), 2.36 (AB system, J ) 16.7
Hz, 2 H), 4.63 (d, J ) 10.2 Hz, 1 H), 6.07 (d, J ) 10.2 Hz, 1 H),
7.20-7.40 (m, 10 H); 13C NMR (63 MHz) δ 22.4, 25.3, 40.6, 44.3,
85.9, 120.9-149.0, 176.2; MS m/z 292 (M+, 24), 207 (100), 165
(27).
1
cm-1; H NMR (300 MHz) δ 1.00 (s, 3 H), 1.17 (s, 3 H), 4.53 (d,
J ) 10.0 Hz, 1 H), 4.86 (d, J ) 2.7 Hz, 1 H), 6.24 (d, J ) 10.0
Hz, 1 H), 6.25 (d, J ) 2.7 Hz, 1 H), 7.20-7.41 (m, 10 H); 13C
NMR (63 MHz) δ 24.1, 27.8, 42.8, 87.6, 112.6, 124.2, 127.3-
129.8, 139.0, 141.6, 143.3, 146.0; MS m/z 276 (M+, 9), 247 (100),
191 (19), 167 (11); HRMS m/z (M+) calcd for C20H20O 276.1509,
1
found 276.1519. Compound 5c: IR (neat) 1720 cm-1; H NMR
(300 MHz) δ 1.17 (s, 3 H), 1.21 (s, 3 H), 3.41 (d, J ) 5.8 Hz, 1
H), 5.90 (d, J ) 5.5 Hz, 1 H), 6.22 (d, J ) 5.5 Hz, 1 H), 7.20-
7.37 (m, 10 H), 9.27 (d, J ) 5.8 Hz, 1 H); 13C NMR (63 MHz) δ
23.7, 30.1, 49.7, 64.2, 66.2, 126.3-147.9, 206.5; MS m/z 277 (M+
+ 1, 45), 276 (M+, 45), 247 (100), 207 (74).
Dir ect Ir r a d ia tion of 3b. Compound 3b (426 mg, 1.45 mmol)
as a mixture 1:2 of cis:trans isomers was irradiated for 10 h.
Flash chromatography using hexane/Et2O (9:1) gave 64 mg (15%)
of 8 and 320 mg (75%) of recovered starting material 3b as a
1:1 mixture of cis:trans isomers. Further elution with Et2O
afforded 41.8 mg (10%) of highly polar material.
Dir ect Ir r a d ia tion of 3c. Compound 3c (288 mg, 1.1 mmol)
as a 1:2 mixture of cis:trans isomers was irradiated for 10 h.
Flash chromatography using hexane/Et2O (95:5) gave 70 mg
(24%) of 2,2-dimethyl-5,5-diphenyl-3-cyclopentene-1-carbalde-
hyde (5c) as a oil and 85 mg (30%) of recovered starting material
3c as a 1:2 mixture of cis:trans isomers. Further elution with
Et2O afforded 111 mg (30%) of highly polar material.
Dir ect Ir r a d ia tion of 3d . Compound 3d (141 mg, 0.49 mmol)
as a 1:2 mixture of cis:trans isomers was irradiated for 3 h 30
min. Flash chromatography using hexane/Et2O (9:1) gave 48 mg
(34 %) of 3d as a 1:2 mixture of cis:trans isomers and 26 mg
(19%) of 5-(2,2-diphenylvinyl)-2-hydroxy-2,4,4-trimethyltetrahy-
drofuran (7) as a white solid and as a 2:1 mixture of the two
possible diastereoisomers A and B. Further elution with Et2O
afforded 45 mg (30%) of highly polar material.
m -Meth oxya cetop h en on e-Sen sitized Ir r a d ia tion of 3d .
Compound 3d (117 mg, 0.40 mmol), as a mixture 1:2 cis:trans
isomers, and m-metoxyacetophenone (109 mg, 0.95 mmol) were
irradiated for 1 h. Flash chromatography using hexane/Et2O (98:
2) gave 29.8 mg (25%) of starting 3d as a 1:1 mixture of cis:
trans isomers, 14.6 mg (13%) of 4-acetyl-3,3-dimethyl-5,5-
diphenyl-1-cyclopentene (5d ) as a oil, 15 mg (13%) of 5-(2,2-
diphenylvinyl)-2-hydroxy-2,4,4-trimethyltetrahydrofuran (7) as
a white solid, and a 2:1 mixture of the two possible diastereo-
isomers A and B. Further elution with Et2O afforded 9 mg (5%)
of highly polar material. Compound 5d : IR (neat) 1680 cm-1
;
1H NMR (300 MHz) δ 1.00 (s, 3 H), 1.26 (s, 3 H), 2.19 (s, 3 H),
3.79 (s, 1 H), 5.73 (d, J ) 5.6 Hz, 1 H), 6.26 (d, J ) 5.6 Hz, 1 H),
7.13-7.35 (m, 10 H); 13C NMR (63 MHz) δ 24.2, 30.0, 32.1, 48.3,
61.0, 63.7, 123.6-148.8, 201.5; MS m/z 290 (M+, 8), 247 (100),
205 (30). Compound 7: mp 120-122 °C (hexane); IR (KBr) 3450-
1
3350 cm-1; H NMR (300 MHz) δ 0.91 (s, 1 H, B-isomer), 0.93
Dir ect Ir r a d ia tion of 3e. The mixture of the four diastereo-
isomers obtained in the synthesis of compound 3e (344.5 mg,
1.2 mmol) was irradiated for 8 h. Flash chromatography using
hexane/Et2O (95:5) gave 66.1 mg (20%) of a 1:1 mixture of cis:
trans isomers of aldehyde 3c, resulting from partial hydrolysis
of the starting oxime, 30.7 mg (9%) of 2,2-dimethyl-5,5-diphenyl-
3-cyclopentene-1-carbaldehyde oxime (5e) as an oil and as a 1:2
mixture of (Z:E) isomers, 21 mg (6%) of 6-(2,2-diphenylvinyl)-
5,5-dimethyl-5,6-dihydro-4H-1,2-oxazine (12) as a oil, and 93 mg
(27%) of 3e as a 2:1 mixture of cis:trans isomers of the (Z)-oxime.
Further elution with Et2O afforded 100 mg (28%) of highly polar
(s, 2 H, A-isomer), 1.09 (s, 2 H, A-isomer), 1.25 (s, 1 H, B-isomer),
1.53 (AB system, J ) 14.7 Hz, 1.33 H, A-isomer), 1.56 (s, 2 H,
A-isomer), 1.72 (d, J ) 13.2 Hz, 0.33 H, B-isomer), 1.88 (s, 1 H,
B-isomer), 1.96 (d, J ) 13.2 Hz, 0.33 H, B-isomer), 2.29 (br s,
0.66 H, A-isomer), 2.57 (br s, 0.33 H, B-isomer), 4.15 (d, J )
10.1 Hz, 0.33 H, B-isomer), 4.42 (d, J ) 9.8 Hz, 0.66 H,
A-isomer), 6.07 (d, J ) 9.8 Hz, 0.66 H, A-isomer), 6.25 (d, J )
10.1 Hz, 0.33 H, B-isomer), 7.20-7.45 (m, 10 H); 13C NMR (63
MHz) δ 23.5, 23.8, 25.8, 27.2, 29.3, 29.4, 42.9, 43.8, 53.1, 53.9,
83.1, 85.7, 103.7, 104.7, 124.6-146.4; MS m/z 291 (M+ -17, 4),
250 (33), 209 (100), 167 (13). Anal. Calcd for C21H24O2: C, 81.8;
H, 7.8. Found: C, 81.99; H, 7.70.
material. Compound 12: IR (neat) 1655 cm-1 1H NMR (300
;
MHz) δ 0.83 (s, 3 H), 1.10 (s, 3 H), 1.90 (d, J ) 3.0 Hz, 2 H),
4.08 (d, J ) 10.0 Hz, 1 H), 6.07 (d, J ) 10.0 Hz, 1 H), 7.14 (t, J
) 3.0 Hz, 1 H), 7.26-7.40 (m, 10 H); 13C NMR (63 MHz) δ 21.1,
26.4, 29.0, 36.6, 80.8, 121-129.7, 147.2; MS m/z 291 (M+, 9),
247 (75), 209 (100), 165 (56).
Acetop h en on e-Sen sitized Ir r a d ia tion of 3e. The mixture
of the four diastereoisomers obtained in the synthesis of
compound 3e (407 mg, 1.4 mmol) and acetophenone (7 g, 59
mmol) were irradiated for 1 h. Flash chromatography using
hexane/Et2O (9:1) gave 83 mg (20%) of 2,2-dimethyl-5,5-diphen-
yl-3-cyclopentene-1-carbaldehyde oxime (5e) as an oil, and as a
6:5 mixture of (Z:E)-isomers, and 194 mg (48%) of the (Z)-isomer
of the starting oxime 3e as a 1:2 mixture of cis:trans isomers.
Further elution with Et2O afforded 76 mg (15%) of highly polar
Dir ect Ir r a d ia tion of 3f. Compound 3f (220 mg, 0.78 mmol)
as a 1:2 mixture of cis:trans isomers was irradiated for 10 h 30
min. Flash chromatography using hexane/Et2O (95:5) gave 42
mg (20%) of (E)-2,2-dimethyl-6,6-diphenyl-3,5-hexadien-1-ol (14)
as a oil and 88 mg (40%) of recovered starting material 3f as a
1:6 mixture of cis:trans isomers. Further elution with Et2O
afforded 80 mg (30%) of highly polar material. Compound 14:
material. Compound 5e: IR (neat) 3220, 1650, 1620 cm-1 1H
;
NMR (300 MHz) δ 0.81 (s, 1.35 H, (E)-isomer), 0.85 (s, 1.65 H,
(Z)-isomer), 1.08 (s, 1.35 H, (E)-isomer), 1.15 (s, 1.65 H, (Z)-
isomer), 3.50 (d, J ) 10.2 Hz, 0.45 H, (E)-isomer), 4.44 (d, J )
9.3 Hz, 0.55 H, (Z)-isomer), 5.80 (d, J ) 5.7 Hz, 0.55 H, (Z)-
isomer), 5.83 (d, J ) 5.7 Hz, 0.45 H, (E)-isomer), 6.02 (d, J )
5.7 Hz, 1 H, (Z:E)-isomers), 6.22 (d, J ) 9.3 Hz, 0.55 H, (Z)-
isomer), 6.85 (d, J ) 10.2 Hz, 0.45 H, (E)-isomer), 7.03-7.35
(m, 10 H), 8.20 (br s, 0.45 H, (E)-isomer), 8.80 (br s 0.55 H, (Z)-
isomer); 13C NMR (63 MHz) δ 23,5 (E)-isomer), 23.8 (Z)-isomer),
29.1 (E)-isomer), 29.7 (Z)-isomer), 49.2 (E)-isomer), 49.5 (Z)-
isomer), 49.9 (Z)-isomer), 55.7 (E)-isomer), 63.6 (E)-isomer), 65.1
(Z)-isomer), 126.1-148.4, 152.9 (Z)-isomer), 153.4 (E)-isomer);
MS m/z 291 (M+, 32), 274 (100), 193 (53), 167 (35); HRMS m/z
(M+) calcd for C20H21NO 291.1619, found 291.1618.
m -Meth oxya cetop h en on e-Sen sitized Ir r a d ia tion of 3f.
Compound 3f (205 mg, 0.73 mmol) as a 1:2 mixture of cis:trans
isomers and m-methoxyacetophenone (362 mg, 2.4 mmol) were
irradiated for 4 h. Flash chromatography using hexane/Et2O (95:
5) as eluent gave 123 mg (60%) of starting material 3f as a 1:2
mixture of cis:trans isomers. Further elution with Et2O afforded
82 mg (30%) of highly polar material.
1
IR (neat) 3620-3590 cm-1; H NMR (300 MHz) δ 0.99 (s, 6 H),
3.34 (d, J ) 5.4 Hz, 2 H), 5.84 (d, J ) 15.3 Hz, 1 H), 6.20 (dd, J
) 15.3, 10.5 Hz, 1 H), 6.67 (d, J ) 10.5 Hz, 1 H), 7,21-7,46 (m,
10 H), (OH signal not observed); 13C NMR (63 MHz) δ 23.9, 39.1,
71.8, 127.0-142.8; MS m/z 278 (M+, 21), 261 (10), 260 (4), 247
(100), 152 (75).
Ack n ow led gm en t. We thank the Direccion General
de Investigacion Cientifica y Tecnica (Grant PB 94/0238)
for financial support. We acknowledge the support
provided by the Centro de Resonancia Magnetica, the
Centro de Microanalisis, and the Servicio de Espec-
trometria de Masas of the Universidad Complutense.
Su p p or tin g In for m a tion Ava ila ble: 1H NMR spectra for
all compounds lacking analyses (16 pages). See any current
masthead page for ordering and Internet access information.
J O981965S