Some reactions of gem-dibromocyclopropanes and metal carbonyls

Article abstract of DOI:10.1002/jccs.201100375

A series of gem-dibromocyclopropanes were treated with various metal complexes. Among the metal complexes, Ru(CO)₂(PPh₃) ₃, Ru(CO)₃(PPh₃)₂, and Mo(CO) ₆ were able to remove a bro

Full text of DOI:10.1002/jccs.201100375

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Article
Some Reactions of gem-Dibromocyclopropanes and Metal Carbonyls
a,
b
a
a
a
Shaw-Tao Lin, * Chuan-Chen Lee, Mei-Fang Ding, David W. Liang and An-Ting Jeng
Department of Applied Chemistry, Providence University, Sha-Lu, Taichung 43301, Taiwan, R.O.C.
a
b
Department of Health and Nutrition Biotechnology, Asia University, Wufong, Taichung 41354, Taiwan, R.O.C.
(Received Jun. 18, 2011; Accepted Oct. 13, 2011; Published Online Oct. 27, 2011; DOI: 10.1002/jccs.201100375)
A series of gem-dibromocyclopropanes were treated with various metal complexes. Among the metal
complexes, Ru(CO)
,1-dibromo-2-phenylcyclopropanes (1) to yield a series of corresponding of 1-bromo-2-phenylcyclo-
propanes (2). Upon the treatment of 1 with Cr(CO) in DMSO, a series of allenes were obtained in good
2 3 3 3 3 2 6
(PPh ) , Ru(CO) (PPh ) , and Mo(CO) were able to remove a bromine atom from
1
6
yields. The correlation between the rate of formation of allenes and the substituents on the benzene gives a
negative coefficient which suggests the dibromocyclopropanes possesses as an electrophile toward to
Cr(CO) . In the presence of Cr(CO) , gem-dibromobicyclo[n,1,0]alkanes (4) in DMF or DMSO solution
6 6
underwent the cleavage of carbon-bromine bond followed by ring-expansion and coupling reaction to
form bicycloalkenes 7.
Keywords: gem-Dibromocyclopropane; Chromium carbonyl; Debromination; Ring-opening; Cou-
pling.
INTRODUCTION
The structure of cyclopropane ring possesses a high
Scheme I
ring strain character. With additional halogen, gem-di-
halocyclopropanes have played an important role in or-
1
ganic synthesis. They are valuable substrates for the
preparation of monohalocyclopropanes, cyclopropanes,
cyclopropenes, allenes, and many other hydrocarbon sys-
2
tems. For example, the versatile chemical intermediate
1
,3,5-cyclohepatriene has been prepared by thermal rear-
Scheme II
3
rangement of 7,7-dihalonorcaranes. Due to their excep-
tional availability, the intensive studies on their chemistry
have been carried out. Aryldihalocyclopropanes were
converted to allenes in the presence of strong bases, such
4
4
5
6
3 4 2
as MeLi , CrCl /LiAlH , SmI and Grignard reagent.
On the fused gem-dihalobicyclo[n.1.0]alkane, the ring ex-
7
pansion was easily undergoing by treatment of silver-ion
8
or under high temperature condition. Low valence metals
RESULTS AND DISCUSSION
are readily used to undergo insertion into the carbon-halo-
In continuing our effort on seeking the application of
cyclopropanes, we used the various lower valence metallic
complexes to activate the 1,1-dibromo-2-phenylcylopro-
pane (1a) and determined the final transformation prod-
ucts. The progress of reaction was monitored by using
GC/MS analysis and the results were summarized in Table
9
gen bond for coupling reaction or reduction. To our best
knowledge, reaction of metal carbonyl and dibromocy-
clopropane has not been described. Herein, we report the
formation of allenes and ring-expansion-coupling prod-
ucts from the treatment of arylcyclopropane (Scheme I)
1
. Among the used metallic complexes, RuCl
W(CO) , and Co (CO) (entries 1~3, 8, 9) in the used sol-
vents were inert; Ru(CO) (PPh , Ru(CO) (PPh and
Mo(CO) (entries 4~7, 10) yielded 1-bromo-2-phenylcy-
2 3 3
(PPh ) ,
and fused cyclopropanes (Scheme II) with Cr(CO)
6
, re-
spectively. Since Cr(CO) is a commercially available,
6
6
2
8
stable in air and inexpensive reagent, it can be useful for
many synthetic methods.
2
3
)
3
3
3 2
)
6
*
Corresponding author. E-mail: sdlin@pu.edu.tw
J. Chin. Chem. Soc. 2012, 59, 529-534
© 2012 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
529

Article
Lin et al.
Table 1. Reaction of 1,1-dibromo-2-phenylcyclopropane with various metallic
complexes
a
Entry
Metallic complex
RuCl (PPh )
Solvent
Temp. °C /time
Product
no reaction
no reaction
2a (trace)
2a (14%)
2a (81%)
2a (90%)
2a (10%)
no reaction
no reaction
2a (20%)
1
2
3
4
5
6
7
8
9
i-PrOH
reflux/3 days
reflux/3 days
130 °C/1 day
reflux/1 day
reflux/3 h
130 °C/12 h
reflux/3 days
130 °C/12 h
130 °C/12 h
130 °C/12 h
130 °C/0.5 h
130 °C/2 h
2
3 3
RuCl (PPh )
CH CN
2
3 3
3
RuCl (PPh )
DMSO
2
3 3
Ru(CO) (PPh )
CH CN
2
3 3
3
Ru(CO) (PPh )
C H
12
2
3 3
6
Ru(CO) (PPh )
DMSO
2
3 3
Ru(CO) (PPh )
CH CN
3
3 2
3
W(CO)6
DMSO
DMSO
DMSO
DMSO
DMSO
Co (CO)8
2
1
1
1
1
1
1
0
1
2
3
4
5
Mo(CO)6
Cr(CO)6
Cr(CO)6
Cr(CO)6
Cr(CO)6
Cr(CO)6
2a (15%) + 3a (53%)
3a (86%)
2a (18%) + 3a (26%)
3a (81%)
b
DMSO
DMF
130 °C/2 h
130 °C/12 h
130 °C/6 h
c
DMSO
2a (32%)
Reactions of dibromocyclopropane 1a (1.0 mmol) and metallic complex (1.0 mmol)
in used solvent (10.0 mL) was carried out at indicated condition.
a
Yields were measured based on the area ratio from crude products by GC/MS
analysis.
b
0
1
.5 mmol of Cr(CO) was used.
,1-Dichloro-2-phenylcyclopropane was used as reactant.
6
c
clopropane (2a). Compound 2a were verified by compar-
ing the retention time from GC analysis and the mass spec-
tra with the authentic compound obtained from reduction
of corresponding dibromocyclopropane 1a using diethyl
no free carbene was detected.
To determine the progress of reaction, the composi-
tion of products were monitored by using GC/MS analysis
and the identities of products were verified by analysis of
their mass spectra. The concentrations of product on vari-
ous reaction times are depicted at Fig. 1. From the figure,
we find that the allene is formed right after the formation of
monobromocyclopropane 2a and its concentration is
higher than that of 2a along the progress of reaction. That
1
0
phosphate and triethylamine. 1a was converted into
allene 3a by treatment of Cr(CO) in DMSO solution in
6
good yield (entries 11, 12). If DMF is used instead of
DMSO, longer reaction time is required to obtain the com-
parable result (entry 14). Half of equivalent amount of
Cr(CO)
6
only converts partial of 1a into allene (entry 13).
was necessary to remove
Equivalent amount of Cr(CO)
6
two bromine atoms from cyclopropane ring for the further
reaction. The gem-dichloro counterpart (entry 15) only un-
derwent reduction with substantial slow reaction rate.
Higher polar aprotic solvent was required for the debro-
mination and formation of allene. The formation of green
precipitates indicated the conversion of Cr(0) into stable
Cr(III) species.
The carbene has been proposed as an intermediate for
1
1
Fig. 1. Concentration of 2a and 3a with time during the
the transformation of dihalocyclopropanes into allene.
We attempted to use cyclohexene as a trapping agent in the
mixture of compound 1a and Cr(CO) . After work-up,
6
reaction of 1a and Cr(CO) at 130 °C. u: 1,1-
dibromo-2-phenylcyclopropane (1a), n: 1-bro-
mo-2-phenylcyclopropane (2a), s: 1,2-Pro-
padienylbenzene (3a). The amounts (yields) of
1a, 2a, and 3a were estimated based on the ar-
eas determined by GC-MS analysis.
6
none of bicyclo[4,1.0]heptane adduct was detected except
allene 3a. The result implied that the formation of allene 3a
from monobromocyclopropane 2a was a rapid process and
530
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CHEMICAL SOCIETY
Reactions of Bromocyclopropanes and Metal Carbonyls
might indicate the rate determining step is the removal of
first bromine atom and the removal of second bromine
along with allene formation is a fast process. The maximum
amount of 2a appears at 25 min.
Table 2. Relative rate for the formation of arylallene from the
reaction of 1,1-dibromo-2-arylcyclopropanes and
Cr(CO) in DMSO at 130 °C
6
+
Compound (R)
s
Relative rate
4
4
3
-OCH (3e)
-0.79
-0.31
-0.07
0
0.11
0.12
0.15
0.37
0.39
1.56
1.30
1.18
1.00
1.07
1.05
0.97
0.90
0.89
During the reaction between low valence metal and
carbon-bromine bond, the metal undergoes an oxidative-
3
-CH (3c)
3
-CH (3b)
1
2
3
addition process (insertion process). The electron density
of carbon-bromine bond would influence on the rate of in-
sertion and/or further process. The substituent on the
phenyl ring can affect the electron-density of the cyclopro-
pane ring. Hammett’s equation is used to demonstrate the
intense of effect on the reaction rate by substituent. In this
work, the competition reactions between 1,1-dibromo-2-
phenylcyclopropane and its substituted counterpart toward
H (3a)
4-Cl (3i)
3
4
3
3
-OCH (3d)
3
-Br (3g)
-Cl (3 h)
-Br (3f)
1
5
solution. The additional isobaric signal can be concluded
as 3-bromocycloheptene 6c by comparing the retention
time of the product from allylic bromination of cyclo-
6
to 0.5 eqv. amount of Cr(CO) in DMSO were executed to
determine the possible mechanism. The reaction mixtures
were heated at 130 °C for 15 min, quenched with ice-water,
extracted with n-hexane followed by GC-MS analysis. The
ratio of allene areas was used to estimate the relative forma-
tion rate. The correlation between the relative rate vs.
1
6
heptene by using N-bromosuccinimde (NBS). The reac-
tant complete disappeared within first hours with formation
of monoboromocyclopropane 5b and bromocycloalkene
6
b. The significantly amount of coupling product formed
+
Hammett constants (s ) of the specific substituent on the
along with vinyl bromide 6b after 3 h. After work-up, the
isolated compounds were subjected to spectral analysis.
The molecular weights of resultant obtained from 4b, 4c
are corresponding to the coupling products and the NMR
spectra of 7b and 7c are consisting with the literature re-
phenyl ring gives r = -0.55 with coefficient of 0.949 (Table
2
, Fig. 2). The small and negative r value implies that the
carbon bearing two bromines accepts a nucleophile,
Cr(CO) , in the initial stage which is influenced by the re-
6
1
3
1
7
mote substituent. The similar effect on that carbon is also
observed from the study of the substituent function of C-13
port. By comparing the pattern of NMR spectrum of 7d
with that of compound 7b and 7c, along with its molecular
weight (m/z 246), we can conclude 7d is also a coupling
product. The product obtained from 4a is different from
other medium ring counterpart. A molecular ion of 7a ap-
pears 320 amu along with the satellites of 318 amu and 322
1
4
chemical shifts.
Same conditions were applied on the on the dibromo-
n,1,0]cycloalkanes (n = 3 ~ 6). The progress of reaction
[
between 7,7-dibromobicylo[4.1.0]heptane (4b) and Cr(CO)
6
was also monitored by using GC/MS analysis (Fig. 3). The
identity of monobromocyclopropane 5b was verified via
the comparison the retention time with product obtained
from reduction of 4a using dimethylphosphite in DMSO
Fig. 3. Concentrations of 5b, 6b, and 7b with time dur-
6
ing the reaction of 4b and Cr(CO) at 130 °C.
u: 7,7-dibromobicyclo[4.1.0]heptane, n: 7-
bromobicyclo[4.1.0]heptane, s: 1-bromocy-
clohept-1-ene, ´: 3-(2-cycloheptenyl)cyclo-
heptene. The amounts (yields) of 4b, 5b, 6b,
and 7b were determined by GC-MS analysis.
Fig. 2. The correlation between relative rate and the
+
Hammett substituent constant (s ) for the for-
mation of arylallenes.
J. Chin. Chem. Soc. 2012, 59, 529-534
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531

Article
Lin et al.
amu with intensities ratio of 1:2:1 that indicates the pres-
dure. The spectral data of those compounds were in good
agreement with the literature report.
1
ence of two bromine atoms. The H NMR spectrum can be
1
9
divided into two set spectra which corresponding to a mix-
1,2-Propadienylbenzene (3a)
1
8
1
ture of its meso- and dl-form with equivalent ratio.
Colorless oil, yield 86%; H NMR: d 5.28 (d, J = 6.8
From Figs. 1 and 3, we are able to observe that a bro-
Hz, 2H), 6.31 (t, J = 6.8 Hz, 1H), 7.32-7.35 (m, 1H),
1
3
mine atom of dibromocyclopropane can be eliminated by
7.45-7.49 (m, 4H); C NMR d 78.8, 93.9, 126.7, 126.8,
.
+
Cr(CO)
6
to form a monobromocyclopropane intermediate,
128.6, 133.9, 209.8; EIMS m/z 116 (M , 61%), 115
which is ruptured at C2-C3 bond leading to allene from
(100%).
1
9
arylcyclopropanes 1. The ring-rupture-coupling products
1-Methyl-3-(1,2-propadienyl)benzene (3b)
1
were obtained from bicycloalkanes 4. Cr(CO)
6
undergoes
Colorless oil, yield 75%; H NMR: d 2.37 (s, 3H),
an oxidative-addition into carbon-bromine to initiate this
5.16 (d, J = 6.8 Hz, 2H), 6.17 (t, J = 6.8 Hz, 2H), 7.04 (d, J =
1
2
13
series process.
7.6 Hz, 1H), 7.06-7.10 (m, 2H), 7.23 (t, J = 7.6 Hz, 1H); C
NMR d 21.3, 78.6, 9.9, 123.8, 127.3, 127.7, 128.5,133.8,
.
+
EXPERIMENTAL
General
138.2, 209.8; EIMS m/z 130 (M , 82%), 115 (100%).
1
9
1-Methyl-4-(1,2-propadienyl)benzene (3c)
1
Experiments were performed under a dry nitrogen at-
Colorless oil, yield 79%; H NMR: d 2.35 (s, 3H),
1
13
mosphere. H and C spectra were recorded at 400, and
00 MHz on Bruker Avance-400, respectively, at ambient
temperature. Chemical shifts for samples in CDCl solution
5.14 (d, J = 6.8 Hz, 2H), 6.16 (t, J = 6.8 Hz, 1H), 7.13 (d, J =
1
3
1
8.0 Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H); C NMR d 21.1,
78.6, 93.7, 126.6, 129.3, 130.9, 136.6, 209.6; EIMS m/z
3
.
+
are reported in d units relative to TMS. High resolution
mass spectra were recorded on a Jeol JMS-HX 110 instru-
ment and low mass spectra were obtained from GC/MS
130 (M , 92%), 115 (100%).
1
9
1-Methoxy-3-(1,2-propadienyl)benzene (3d)
1
Colorless oil; yield 72%; H NMR d 3.81 (s, 3H), 5.15
(d, J = 6.8 Hz, 2H), 6.14 (t, J = 6.8 Hz, 1H), 6.76 (dd, J =
7.6, 2.0 Hz, 1H), 6.86 (d, J = 2.0 Hz, 1H), 6.89 (d, J = 7.6
(
Thermo Focus GC coupled with Thermo Polaris Q) at an
ionization potential of 70 eV. A capillary column (Varian,
CP-Sil 5 CB, 25 m ´ 0.25 mm ID) was used to separate the
mixture for mass analysis. All dihalocyclopropanes were
prepared by the reaction of haloform and corresponding
1
3
Hz, 1H), 7.22 (t, J = 7.6 Hz, 1H); C NMR d 55.2, 78.8,
93.9, 111.8, 112.7, 119.4, 129.5, 135.4, 159.8, 209.8; EIMS
.
+
m/z 146 (M , 100%), 103 (77%).
t 14
19
alkene in n-hexane with presence of KOBu . 7-Bromo-
1-Methoxy-4-(1,2-propadienyl)benzene (3e)
1
bicyclo[4.1.0]cycloheptane was prepared by reducing of
Colorless oil, yield 95%; H NMR d 3.78 (s, 3H), 5.10
1
5
7
,7-dibromobicyclo[4.1.0]heptane according to literature
(d, J = 6.8 Hz, 2H), 6.11 (t, J = 6.8 Hz, 1H), 6.83 (d, J = 8.8
1
3
and 3-bromocycloheptene was obtained by allylic bro-
Hz, 2H), 7.20 (d, J = 8.8 Hz, 2H); C NMR d 55.21, 78.62,
93.27, 114.08, 126.05, 127.67, 158.66, 209.29; EIMS m/z:
1
6
mination of cycloheptene by NBS. All used solvents were
dried and degassed prior to reaction. All reagents were
commercially available and used as purchased.
.
+
146 (M , 100%), 103 9 (86%).
1
9
1-Bromo-3-(1,2-propadienyl)benzene (3f)
1
General procedure for the reaction of 1,1-dibromo-
Colorless oil, yield 78%; H NMR d 5.19 (d, J = 6.8
2
-phenylcyclopropanes (1a) and Cr(CO)
A mixture of dibromocyclopropane (1.0 mmol) and
Cr(CO) (1.0 mmol) in various solvent (10 mL) in a 25-mL
6
Hz, 2H), 6.10 (t, J = 6.8 Hz, 1H), 7.14-7.25 (m, 2H), 7.32
1
3
(d, J = 7.6 Hz, 1H), 7.45 (s, 1H); C NMR d 79.4, 92.9,
122.7, 125.2, 129.4, 129.7, 130.0, 136.2, 209.9; EIMS m/z
6
.
+
round-flask on an oil-bath was stirred at 130 °C. Upon the
progress of reaction, the color of solution become to green
color indicated the consumption of Cr(0) complex. After
reaction was completed, the mixture was then poured into
an ice-water (20 mL) and extracted with n-hexane (20 mL´
196 (M , 28%), 115 (100%).
1
9
1-Bromo-4-(1,2-propadienyl)benzene (3g)
1
Colorless oil, yield 84%; H NMR d 5.15 (d, J = 6.8
Hz, 2H), 6.11 (t, J = 6.8 Hz, 1H), 7.16 (d, J = 8.4 Hz, 2H),
1
3
7.41 (d, J = 8.4 Hz, 2H); C NMR d 79.2, 93.2, 120.5,
.
+
3
). The organic layer was washed with water, dried (MgSO
4
)
128.2, 131.7, 132.9, 209.8; EIMS m/z 196 (M , 32%), 115
and then separated by a silica gel column using n-hexane as
eluent to give the desired product.
(100%).
2
0
1-Chloro-3-(1,2-propadienyl)benzene (3h)
1
Products 3a-3i were obtained according to this proce-
Colorless oil, yield 83%; H NMR d 5.18 (d, J = 6.8
532
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JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Reactions of Bromocyclopropanes and Metal Carbonyls
Hz, 2H), 6.11 (t, J = 6.8 Hz, 1H), 7.15-7.25 (m, 3H), 7.29
2H), 3.15-3.25 (m, 2H), 6.11-6.18 (m, 2H), 6.20-6.28 (m,
1
3
13
(
s, 1H); C NMR d 79.3, 93.1, 124.8, 126.5, 126.8, 128.7,
2H); C NMR d 21.4, 21.5, 24.4, 27.7, 27.9, 28.8, 44.2,
.
.
+
+
1
34.5, 135.9, 209.9; EIMS m/z 152 (M , 11%), 115
45.7, 127.0, 127.3, 131.9, 132.7; EIMS m/z 322/320 (M ,
(
100%).
-Chloro-4-(1,2-propadienyl)benzene (3i)
3%/3%), 79 (100%).
2
0
17
1
3-(2-Cycloheptenyl)cycloheptene (7b)
1
1
Colorless oil, yield 89%; H NMR d 5.16 (d, J = 6.8
Hz, 2H), 6.13 (t, J = 6.8 Hz, 1H), 7.22 (d, J = 8.4 Hz, 2H),
Colorless oil, yield 84%; H NMR d 1.00-2.40 (m,
1
3
18H, 5.50-5.70 (m, 2H), 5.70-5.90 (m, 2H); C NMR d
1
3
7
1
.27 (d, J = 8.4 Hz, 2H); C NMR d 79.2, 99.1, 127.8,
26.9, 28.7, 30.5, 31.0, 31.3, 31.4, 45.4, 45.9, 131.5, 131.8,
.
.
+
+
28.7, 132.4, 132.5, 209.8; EIMS m/z 152 (M , 12%), 115
136.3, 136.6; EIMS m/z 190 (M , 0.3%), 95 (100%).
1
7
(
100%).
3-(2-Cycloocteyl)cyclooctene (7c)
1
Attempt to trap the carbene by adding cyclohexene
into mixture of dibromocyclopropane (1a) and
Colorless oil, yield 75%; H NMR d 0.80-2.50 (m,
1
3
22H), 5.20-5.40 (m, 2H), 5.60-5.75 (m, 2H); C NMR d
Cr(CO)
6
25.8, 25.9, 26.8, 26.8, 27.1, 27.1, 28.6, 29.5, 29.7, 34.3,
.
+
The experiment was carried out as previous process
except for adding cyclohexene (2.0 mmole). After work-
up, allene 3a was observed as only product presence in re-
sultant from the analysis used GC/MS technique.
40.7, 40.9, 129.2, 129.4,133.3, 134.4; EIMS m/z 218 (M ,
3%), 67 (100%).
3-(2-Cyclononeyl)cyclononene (7d)
1
Colorless oil, yield 80%; H NMR d 1.00-2.50 (m,
1
3
Competition reaction between Cr(CO)
6
toward to
26H), 5.10-5.30 (m, 2H), 5.40-5.65 (m, 2H); C NMR d
1
1
,1-dibromo-2-phenylcyclopropane and substituted
24.8, 24.9, 25.6, 25.8, 26.0, 26.1, 26.1, 26.4, 26.5, 42.0,
.
+
,1-dibromo-2-phenylcyclopropane in DMSO solution
42.5, 128.8, 129.2, 134.0, 134.9; EIMS m/z 246 (M , 2%),
The mixture of 1,1-dibromo-2-phenylcyclopropane
81 (100%); HRMS calcd for C18
246.1262.
H30 246.2348, found
(
127 mg, 0.50 mmol), substituted 1,1-dibromo-2-phenyl-
cyclopropane (0.50 mmol) and Cr(CO) (1.00 mmol) in
6
DMSO (10.0 mL) with a stir bar in a 25-mL round-bottom
flask was put on a pre-heated (130 °C) oil-bath. After 15
min, the resultant was poured into an ice-water (20 mL).
The mixture was extracted with n-hexane, followed by
ACKNOWLEDGEMENTS
Financial support by the National Science of the Re-
public of China (NSC 94-2113-M-126-005) and the tech-
nique supporting by NCHC are gratefully acknowledged.
4
dried over MgSO and subjected to be analyzed by GC/MS.
The ratio of area of two allenes was used to estimate their
relative rate of formation.
REFERENCES
1. (a) Kirmse, W. Carbene, Carbenoide and Carbenanaloge;
Verlag Chemie: Weinheim, 1969; (b) Weyerstahl, P. In The
Chemistry of Functional Groups; Patai, S.; Rappoport, Z.,
Eds.; John Wiley & Sons: New York, 1983; Supplement D,
pp 1452-1497.
General procedure for the reaction of 1,1-dibromo-
bicyclo[n.1.0]alkane 4 and Cr(CO)
A mixture of dibromocyclopropane 4 (1.0 mmol) and
Cr(CO) (1.0 mmol) in DMF (10 mL) in a 25-mL round-
6
in DMF solution
6
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progress of reaction, the color of solution become to green
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4
MgSO ) and then separated by pass through a silica gel
4
4, 1130.
column using n-hexane as eluent to give the desired prod-
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with the literature report.
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8
2
-Bromo-3-(2¢-bromo-2¢-cyclohexeyl)cyclohexene (7a)
1
6
Colorless oil, yield 87%; H NMR d 1.42-1.65 (m,
8
H), 1.65-1.95 (m, 8H), 1.95-2.15 (m, 8H), 2.82-2.95 (m,
J. Chin. Chem. Soc. 2012, 59, 529-534
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J. Chin. Chem. Soc. 2012, 59, 529-534