Wittig reaction with ion-supported Ph3P

Article abstract of DOI:10.1016/j.tet.2010.11.111

Ion-supported Ph₃P, 4-(diphenylphosphino)benzyltrimethylammonium bromide A and N-methyl-N-[4-(diphenylphosphino)benzyl]pyrrolidinium bromide B, were used for the Wittig reaction. Ion-supported phosphonium salts A1 and B1, which were prepared from the reactions of ion-supported Ph₃P A and B with ethyl bromoacetate, respectively, reacted with aromatic and aliphatic aldehydes in the presence of K₂CO₃ to give the corresponding α,β-unsaturated ethyl esters in good yields with high purity by simple filtration of the reaction mixture and subsequent removal of the solvent from the filtrate. Similarly, ion-supported phosphonium salts A2 and B2, which were prepared from the reactions of ion-supported Ph₃P A and B with p-methylbenzyl bromide, respectively, reacted with aromatic and aliphatic aldehydes in the presence of NaH to provide the corresponding p-methylstyrene derivatives in good yields with high purity by simple filtration of the reaction mixture and the subsequent removal of the solvent from the filtrate. In both reactions, the co-product, ion-supported Ph₃PO, could be obtained quantitatively by simple filtration, and was converted into the corresponding ion-supported Ph₃P A and B again in high yields using dimethyl sulfate, followed by the reduction with LiAlH₄. Recovered and regenerated ion-supported Ph₃P A and B could be reused for the same Wittig reaction while maintaining good yields of ethyl (E)-3-(4′-chlorophenyl)-2-propenoate and 1-(4′-chlorophenyl)-2- (4″-methylphenyl)ethene with high purity by simple filtration and removal of the solvent from the filtrate.

Full text of DOI:10.1016/j.tet.2010.11.111

Tetrahedron 67 (2011) 951e957
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Wittig reaction with ion-supported Ph3P
*
Naoya Shimojuh, Yumi Imura, Katsuhiko Moriyama, Hideo Togo
Graduate School of Science, Chiba University, Yayoi-cho 1-33, Inage-Ku, Chiba 263-8522, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Ion-supported Ph3P, 4-(diphenylphosphino)benzyltrimethylammonium bromide A and N-methyl-N-[4-
(diphenylphosphino)benzyl]pyrrolidinium bromide B, were used for the Wittig reaction. Ion-supported
phosphonium salts A1 and B1, which were prepared from the reactions of ion-supported Ph3P A and B
with ethyl bromoacetate, respectively, reacted with aromatic and aliphatic aldehydes in the presence of
Received 10 November 2010
Received in revised form 30 November 2010
Accepted 30 November 2010
Available online 7 December 2010
K2CO3 to give the corresponding a,b-unsaturated ethyl esters in good yields with high purity by simple
filtration of the reaction mixture and subsequent removal of the solvent from the filtrate. Similarly, ion-
supported phosphonium salts A2 and B2, which were prepared from the reactions of ion-supported Ph3P
A and B with p-methylbenzyl bromide, respectively, reacted with aromatic and aliphatic aldehydes in the
presence of NaH to provide the corresponding p-methylstyrene derivatives in good yields with high
purity by simple filtration of the reaction mixture and the subsequent removal of the solvent from the
filtrate. In both reactions, the co-product, ion-supported Ph3PO, could be obtained quantitatively by
simple filtration, and was converted into the corresponding ion-supported Ph3P A and B again in high
yields using dimethyl sulfate, followed by the reduction with LiAlH4. Recovered and regenerated ion-
supported Ph3P A and B could be reused for the same Wittig reaction while maintaining good yields of
ethyl (E)-3-(40-chlorophenyl)-2-propenoate and 1-(40-chlorophenyl)-2-(400-methylphenyl)ethene with
high purity by simple filtration and removal of the solvent from the filtrate.
Ó 2010 Elsevier Ltd. All rights reserved.
1. Introduction
the pure state. This is the major drawback of using triphenyl-
phosphine. To solve this problem, we recently reported the first
Triphenylphosphine (Ph3P) is one of the most important re-
agents, because it can be used for various types of reactions, such as
the bromination, iodination, and chlorination of alcohols with
carbon tetrabromide (CBr4), molecular iodineeimidazole (I2/imid-
azole), and carbon tetrachloride (CCl4) (the Appel reaction), re-
spectively, and the esterification of carboxylic acids with alcohols in
the presence of diethyl azodicarboxylate (DEAD) (the Mitsunobu
reaction).1,2 The Wittig reaction also requires triphenylphosphine
to form carbonecarbon double bonds through the formation of
phosphonium ylides and the subsequent reaction with aldehydes
or ketones.3 Moreover, it can be used as a ligand for Pd-catalyzed
CeC bond formation (the MizorokieHeck reaction,4a,b the Sono-
gashira reaction,4c the Stille reaction,4d,e and the SuzukieMiyaura
reaction4f,g). However, in the halogenation of alcohols with Ph3P/
CBr4, Ph3P/I2/imidazole, or Ph3P/CCl4, the esterification and ami-
dation of carboxylic acids with Ph3P/DEAD or Ph3P/di(2-pyridyl)
disulfide, and the Wittig reaction, a stoichiometric amount of
Ph3PO is formed as a co-product and it must be removed carefully
by troublesome column chromatography to obtain the product in
preparation of ion-supported Ph3P, 4-(diphenylphosphino)benzyl-
trimethylammonium bromide A, and N-methyl-N-[4-(diphenyl-
phosphino)benzyl]pyrrolidinium bromide B, and their synthetic
utility in the halogenation of alcohols and the esterification of
carboxylic acids as an equivalent required reagent, and the Mizor-
okieHeck reaction and the Sonogashira reaction as a catalytic
amount of ligand with Pd(OAc)2 or PdCl2.5
Here, as part of our study of the synthetic use of ion-supported
Ph3P, we would like to report the Wittig reaction of aromatic and
aliphatic aldehydes with ion-supported phosphoniumylides derived
from ion-supported Ph3P, 4-(diphenylphosphino)benzyl-trimethy-
lammonium bromide A, and N-methyl-N-[4-(diphenylphosphino)
benzyl]pyrrolidinium bromide B.
2. Results and discussion
Ion-supported Ph3P A and B were prepared easily in 74% yield
(three steps) and 54% yield (four steps), respectively, from com-
mercially available chlorodiphenylphosphine using our previous
method.5 First, ion-supported phosphonium salts A1 and B1, which
are the precursors of stabilized ylides, were prepared from the re-
action of ethyl bromoacetate with ion-supported Ph3P A and B in
* Corresponding author. Tel.: þ81 43 290 2792; fax: þ81 43 290 2874; e-mail
address: togo@faculty.chiba-u.jp (H. Togo).
0040-4020/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2010.11.111

952
N. Shimojuh et al. / Tetrahedron 67 (2011) 951e957
95% yield and 100% yield, respectively. Then, both phosphonium
salts A1 and B1 were treated with aromatic and aliphatic aldehydes
in the presence of potassium carbonate in dichloromethane to
regenerated, ion-supported phosphonium salts A1 and B1 could be
prepared in high yields again, and they could be reused for the
same reaction with p-chlorobenzaldehyde to provide ethyl p-
chlorocinnamate in good yields while keeping a high purity until
the second reuse (entries 2, 3 and 13, 14). On the other hand, when
provide the corresponding
yields with high (E)-selectivity, as shown in Table 1. Here, after the
reaction, the reaction mixture was filtered. -Unsaturated ethyl
a,b-unsaturated ethyl esters in good
a,
b
Ph3P was used under the same conditions, a,b-unsaturated ethyl
esters were obtained in high yields with high purity (>90%) after
simple removal of the solvent from the filtrate (entries 1, 5e9, 12,
ester was obtained in good yield, however, the purity was ap-
proximately 43% and Ph3PO was recovered in only 50% yield (entry
15, 16, and 18). Thus, it is very easy to purify the
a
,b
-unsaturated
4). Although phosphonium salts A1 and B1 reacted with a,a,a-tri-
ethyl esters. Moreover, ion-supported Ph3PO, the co-product of
both reactions with ion-supported phosphonium salts A1 and B1,
was recovered by the above filtration in 92e100% yields. The re-
covered ion-supported Ph3PO was treated with dimethyl sulfate,
followed by the reduction with LiAlH4 to regenerate ion-supported
Ph3P A and B in high yields.6 Once ion-supported Ph3P A and B were
fluoroacetophenone in good yields with high purity (entries 10 and
20), they did not react with acetophenone at all (entries 11 and 21),
as that of phosphonium salt derived from Ph3P did not react with
ketones.
Then, ion-supported phosphonium salts A2 and B2, which are
the precursors of semistabilized ylides, were prepared from the
Table 1
Witting reaction with ion-supported Ph3P
Substrate
A
B
Entry
Time (h)
Yielda (%)
Purityb (%)
E/Z
Entry
Time (h)
Yielda (%)
Purityb (%)
E/Z
1
8
8
8
8
94
95
92
99
97
97
97
43
96:4
96:4
96:4
96:4
12
8
8
8
98
95
91
98
90
90
94:6
96:4
96:4
2c
3d
4e
13c
14d
5
6
10
50
95
98
98
97
97:3
96:4
15
16
8
96
91
90
90
96:4
95:5
24
CH3(CH2)6CHO
7
24
100
97
97:3
17
20
90
86
93:7
8
24
24
24
93
92
92
89
90
90
90:10
95:5
18
19
20
20
16
24
92
88
95
95
80
97
92:8
94:6
88:12
9
10
88:12
11
24
0
d
21
48
0
d
d
a
Isolated yield of E and Z alkenes. Ion-supported Ph3PO was recovered in 92∼100% yields.
Purity of product after removal of solvent from the extracts.
The first regenerated ion-supported Ph3P A or B was used.
The second regenerated ion-supported Ph3P A or B was used.
Ph3P was used instead of ion-supported Ph3P A or B, and Ph3PO was recovered in 50% yield.
b
c
d
e

N. Shimojuh et al. / Tetrahedron 67 (2011) 951e957
953
reaction of p-methylbenzyl bromide with ion-supported Ph3P A
and B in 95% yield and 100% yield, respectively. Both phosphonium
salts A2 and B2 were treated with aromatic and aliphatic aldehydes
in the presence of sodium hydride in 1,2-dimethoxyethane or tol-
uene at warming conditions. To a 1,2-dimethoxyethane solution of
ion-supported phosphonium salt A2 or a toluene solution of ion-
supported phosphonium salt B2 was added sodium hydride at 0 ꢀC.
After the mixture was stirred for 1 h at room temperature, aromatic
or aliphatic aldehyde was added to the mixture at 0 ꢀC and the
whole mixture was warmed at 60e70 ꢀC to give p-methylstyrene
derivative in good yield, as shown in Table 2. Then, after the re-
action, the reaction mixture was filtered. p-Methylstyrene de-
rivatives were obtained in high yields with high purity (>90%) and
moderate (E)-selectivity after simple removal of the solvent from
the filtrate (entries 1, 5e8,12,15, 16, and 18). This is again proof that
it is very easy to obtain pure p-methylstyrene derivatives. More-
over, ion-supported Ph3PO, the co-product of both reactions with
ion-supported phosphonium salts A2 and B2 was recovered by the
above filtration in 93e100% yields. The recovered ion-supported
Ph3PO was treated with dimethyl sulfate, followed by reduction
with LiAlH4 to regenerate ion-supported Ph3P A and B in high
yields. Ion-supported phosphonium salts A2 and B2 derived from
the reaction of regenerated ion-supported Ph3P A and B with p-
methylbenzyl bromide were prepared in high yields again and
could be reused for the same reaction with p-chlorobenzaldehyde
to provide 1-(40-chlorophenyl)-2-(400-methylphenyl)ethene in good
yields while keeping a high purity until the second reuse (entries 2,
3, and 13, 14).
When Ph3P was used under the same conditions, 1-(40-chloro-
phenyl)-2-(400-methylphenyl)ethene was obtained in good yield.
However, the purity was approximately 46% and Ph3PO was re-
covered in only 46% yield (entry 4).
Finally, ion-supported phosphonium salts A3 and B3, which are
the precursors of unstabilized ylides, were prepared in 95% and
100% yields, respectively, from the reaction of ion-supported Ph3P A
and B with n-butyl bromide at 100 ꢀC for 50 h. Then, they were
Table 2
Witting reaction with ion-supported Ph3P
Substrate
A
B
Entry
Time (h)
Yielda (%)
Purityb (%)
E/Z
Entry
Time (h)
Yielda (%)
Purityb (%)
E/Z
1
8
8
8
9
95
94
92
90
95
95
95
46
75:25
75:25
75:25
50:50
12
9
9
9
91
90
90
90
85
81
75:25
75:25
75:25
2c
3d
4e
13c
14d
5
6
10
50
95
91
95
96
75:25
79:21
15
16
9
100
90
90
95
78:28
81:19
24
CH3(CH2)6CHO
7f
24
86
91
71:29
17f
24
77
70
74:26
8f
9
24
24
91
71
94
64
90:10
78:22
18
24
24
82
85
90
56
84:16
74:29
68:32
d
19f
10
11
50
50
79
67
91:9
20f
21f
24
24
65
90
Trace
d
d
Trace
d
a
Isolated yield of E and Z alkenes. Ion-supported Ph3PO was recovered in 93∼100% yields.
Purity of product after removal of solvent from the extracts.
The first regenerated ion-supported Ph3P A or B was used.
The second regenerated ion-supported Ph3P A or B was used.
Ph3P was used instead of ion-supported Ph3P A or B, and Ph3PO was recovered in 46% yield.
NaNH2 was used instead of NaH.
b
c
d
e
f

954
N. Shimojuh et al. / Tetrahedron 67 (2011) 951e957
treated with p-chlorobenzaldehyde in the presence of sodium
amide under the same procedure and conditions shown in Table 2,
to give 1-(40-chlorophenyl)-1-pentene in good yields with high
purity after simple filtration of the reaction mixture and removal of
the solvent. In both reactions, ion-supported Ph3PO was recovered
in high yields and ion-supported Ph3P A and B could be regenerated
by the reaction of ion-supported Ph3PO with dimethyl sulfate and
LiAlH4 using the same procedure as that mentioned above. Phos-
phonium salts A3 and B3 could be reused for the same reaction
with p-chlorobenzaldehyde. Although the yield and purity of 1-(40-
chlorophenyl)-1-pentene were gradually decreased as shown in
Scheme 1, ion-supported Ph3PO from both reactions was recovered
by the above filtration in 94e100% yields. The reason may be the
fact that the formation of phosphonium salts A3 and B3 requires
a high temperature and a long reaction time, and the Wittig re-
action with them is not very efficient. Thus, the present ion-sup-
ported Ph3P A and B are not very efficient reagents for the Wittig
reaction with alkylphosphonium salts, such as A3 and B3, which are
derived from the reaction of ion-supported Ph3P A and B with alkyl
halides. When Ph3P was used with n-butyl bromide and then p-
chlorobenzaldehyde in the presence of sodium amide under the
same procedure and conditions, 1-(40-chlorophenyl)-1-pentene
was obtained in 80% yield with 40% purity, and Ph3PO was re-
covered in only 20% yield.
presence of K2CO3 to give the corresponding a,b-unsaturated ethyl
esters in good yields with high purity by simple filtration of the
reaction mixture and subsequent removal of the solvent from the
filtrate. Similarly, ion-supported phosphonium salts A2 and B2,
which were prepared from the reactions of ion-supported Ph3P A
and B with p-methylbenzyl bromide, respectively, and are the
precursors of semistabilized ylides, reacted with aromatic and ali-
phatic aldehydes in the presence of NaH to provide the corre-
sponding p-methylstyrene derivatives in good yields with high
purity by simple filtration of the reaction mixture and subsequent
removal of the solvent from the filtrate. In both reactions, the
co-product, ion-supported Ph3PO, could be obtained quantitatively
by simple filtration and was converted into the corresponding ion-
supported Ph3P A and B again in high yields using dimethyl sulfate,
followed by the reaction with LiAlH4. Recovered and regenerated
ion-supported Ph3P A and B could be reused for the same Wittig
reaction while maintaining good yields of
a,b-unsaturated ethyl
esters and p-methylstyrene derivatives, respectively, with high
purity by simple filtration and removal of the solvent from the
filtrate.
4. Experimental section
4.1. General
1H NMR and 13C NMR spectra were obtained with JEOL-JNM-
ECX400, JEOL-JNM-ECS400, and JEOL-JNM-ECA500 spectrometers.
Chemical shifts are expressed in parts per million downfield from
3. Conclusion
Ion-supported phosphonium salts A1 and B1, which were pre-
pared from the reactions of ion-supported Ph3P A and B with ethyl
bromoacetate, respectively, and are the precursors of stabilized
ylides, reacted with aromatic and aliphatic aldehydes in the
TMS in d units. Mass spectra were recorded on JMS-T100GCV, JMS-
HX110, and Thermo LTQ Orbitrap spectrometers. IR spectra were
measured with a JASCO FT/IR-4100 spectrometer. Melting points
were determined with a Yamato Melting Point Apparatus Model
MP-21. Silica gel 60 (Kanto Kagaku Co.) was used for column
chromatography and Wakogel B-5F was used for preparative p-TLC.
4.2. Typical procedure for the Wittig reaction with ion-
supported Ph3P A1
To a solution of ethyl bromoacetate (1.51 g, 9.0 mmol) in 1,2-
dichloroethane (30 mL) was added 4-(diphenylphosphino)benzyl-
trimethylammonium bromide A (1.88 g, 4.5 mmol). The obtained
mixture was stirred for 2 h at 60 ꢀC. After the reaction, ether was
added and the mixture was stirred for 10 min at room temperature.
Then, the mixture was filtered and washed with ether. Removal of
the solvent from the filtrate gave phosphonium salt A1 in 95% yield.
The obtained phosphonium salt A1 (358 mg, 0.6 mmol) was dried
by a vacuum pump for 2 h at 70 ꢀC. To the flask containing phos-
phonium salt A1 was added a solution of p-chlorobenzaldehyde
(70 mg, 0.5 mmol) in dichloromethane (4 mL) and K2CO3 (138 mg,
1.0 mmol). The obtained mixture was stirred for 8 h at 40 ꢀC under
an argon atmosphere. After the reaction, ether (5 mL) was added
and the obtained mixture was filtered and washed with ether.
Removal of the solvent from the filtrate gave ethyl 3-(40-chlor-
ophenyl)propenoate (E/Z¼96:4) in the crude state. The purity was
estimated by 1H NMR and was 97%. Pure ethyl 3-(40-chlorophenyl)
propenoate was obtained in 94% yield by short flash column
chromatography on silica gel (hexane/AcOEt¼5:2). The co-product,
4-(diphenylphosphono)benzyltrimethylammonium bromide, was
recovered by the above filtration in 98% yield.
4.3. Typical procedure for the Wittig reaction with ion-
supported Ph3P A2
To a solution of 4-methylbenzyl bromide (1.67 g, 9.0 mmol) in 1,2-
dichloroethane (30 mL) was added 4-(diphenylphosphino)benzyl-
trimethylammonium bromide A (1.88 g, 4.5 mmol). The obtained
Scheme 1. Witting reaction with ion-supported phosphonium salts A3 and B3.

N. Shimojuh et al. / Tetrahedron 67 (2011) 951e957
955
mixture was stirred for 2 h at 60 ꢀC. After the reaction, ether was
added and the mixture was stirred for 10 min at room temperature.
Then, the mixture was filtered and washed with ether. Removal of the
solvent from the filtrate gave phosphonium salt A2 in 95% yield. The
obtained phosphonium salt A2 (360 mg, 0.6 mmol) was dried by
a vacuum pump for 2 h at 70 ꢀC. To the flask containing phosphonium
salt A2 were added NaH (44 mg,1.0 mmol) and 1,2-dimethoxyethane
(2 mL). Theobtainedmixturewasstirred for1 hat0 ꢀCunderanargon
atmosphere. After the reaction, p-chlorobenzaldehyde (70 mg,
0.5 mmol) and 1,2-dimethoxyethane (2 mL) were added and the
obtained mixture was stirred for 8 h at 60 ꢀC under an argon atmo-
sphere. After the reaction, acetic acid (5 mL) was added and the
obtainedmixturewas filteredandwashedwithaceticacid. Removalof
the solvent from the filtrate gave 1-(40-chlorophenyl)-2-(400-methyl-
phenyl)ethene (E/Z¼75:25) in the crude state. The purity was esti-
135.04 (t), 138.26 (q),138.29 (q); HRMS (ESI) calcd for C30H34Br2NP
[Mþ]: 597.0801. Found: 597.0756.
4.4.3. Phosphonium salt A3. Mp 162e165 ꢀC; IR (Nujol): 1438, 1297,
1411, 1114, 996, 824, 750, 724, 692 cmꢁ1 1H NMR (400 MHz,
;
CDCl3):
3.53e3.62 (m, 2H), 5.45 (s, 2H), 7.71e7.74 (m, 4H), 7.79e7.86 (m,
8H), 8.26e8.31 (m, 2H); 13C NMR (100 MHz, DMSO):
d¼0.84e0.97 (m, 3H), 1.56e1.68 (m, 4H), 3.46 (s, 9H),
d¼13.8 (p),
20.8 (s), 23.6 (s), 24.3 (s), 52.6 (p), 66.8 (s), 118.4 (q), 119.3 (q), 120.8
(q), 121.6 (q), 130.7 (t), 130.9 (t), 134.2 (t), 134.3 (t), 134.6 (t), 134.7
(t), 134.8 (t), 134.9 (t); HRMS (ESI) calcd for C26H34Br2NP [Mþ]:
549.0796. Found: 547.0770.
4.5. Typical procedure for the Wittig reaction with ion-
supported Ph3P B1
1
mated by H NMR and was 95%. Pure 1-(40-chlorophenyl)-2-(400-
methylphenyl)ethenewas obtained in95% yield byshort flash column
chromatography on silica gel (hexane/CHCl3¼1:4). The co-product,
4-(diphenylphosphono)benzyltrimethylammonium bromide, was
recovered by the above filtration in 97% yield.
Ethyl bromoacetate (1.67 g, 10.0 mmol) or 4-methylbenzyl bro-
mide (1.85 g, 10.0 mmol) was added to a flask containing 1-methyl-
3-[40-(diphenylphosphino)benzyl]pyrrolidinium bromide (2.20 g,
5.0 mmol) in 1,2-dichloromethane (8 mL) at 0 ꢀC. The obtained
mixture was stirred for 24 h at 40 ꢀC under an argon atmosphere.
After the reaction, ether (20 mL) was added and the obtained
mixture was stirred for 30 min at 0 ꢀC. Then, the mixture was fil-
tered and washed with ether. Removal of the solvent from the fil-
trates gave phosphonium salt B1 or B2, in 100% yield. A mixture of
phosphonium salt B1 and K2CO3 (277 mg, 2.0 mmol) in a flask was
dried by a vacuum pump for 2 h at 70 ꢀC. To the flask containing
phosphonium salt B1 and K2CO3 was added a solution of 4-chloro-
benzaldehyde (141 mg, 1.0 mmol) in dichloromethane (5 mL). The
obtained mixture was stirred for 8 h at 40 ꢀC under an argon at-
mosphere. After the reaction, ether (10 mL) was added and the
obtained mixture was stirred for 10 min at 0 ꢀC. Then, the mixture
was filtered and washed with ether. Removal of the solvent from the
filtrate gave ethyl 3-(4-chlorophenyl)acrylate (E/Z¼94:6) in 98%
purity, which was estimated by 1H NMR. Pure ethyl 3-(4-chlor-
ophenyl)acrylate was obtained in 98% yield by short flash
column chromatography on silica gel (AcOEt/hexane¼10:1). The co-
product, N-methyl-N-[4-(diphenylphosphono)benzyl]pyrrolidinium
bromide, was recovered by the above filtration in 98% yield.
4.4. Typical procedure for the Wittig reaction with ion-
supported Ph3P A3
To a solution of 1-bromobutane (1.90 g, 14 mmol) in 1,2-di-
chloroethane (4.0 mL) was added 4-(diphenylphosphino)benzyl-
trimethylammonium bromide (A) (1.90 g, 4.5 mmol). The obtained
mixture was stirred for 50 h at 95 ꢀC. After the reaction, ether was
added and the mixture was stirred for 10 min at room temperature.
Then, the mixture was filtered and washed with ether. Removal of
the solvent from the filtrate gave phosphonium salt A3 in 95% yield.
The obtained phosphonium salt A3 (358 mg, 0.65 mmol) was dried
by a vacuum pump for 2 h at 70 ꢀC. To the flask containing phos-
phonium salt A3 were added NaNH2 (43 mg, 1.0 mmol) and 1,2-
Dimethoxyethane (2 mL). The obtained mixture was stirred for 2 h
at 0 ꢀC under an argon atmosphere. After the reaction, p-chlor-
obenzaldehyde (70 mg, 0.5 mmol) in 1,2-Dimethoxyethane (2 mL)
was added to the mixture at room temperature and the obtained
mixture was stirred for 50 h at 60 ꢀC under an argon atmosphere.
After the reaction, acetic acid (5 mL) was added and the obtained
mixture was filtered and washed with acetic acid. Removal of
the solvent from the filtrate gave 1-(4-chlorophenyl)-1-pentene
(E/Z¼27:73) in the crude state. The purity was estimated by 1H NMR
and was 74%. Pure 1-(4-chlorophenyl)-1-pentene was obtained in
75% yield by column chromatography on silica gel (hexane/
CHCl3¼1:4). The co-product, 4-(diphenylphosphono)benzyl-
trimethylammonium bromide, was recovered by the above filtra-
tion in 98% yield.
4.6. Typical procedure for the Wittig reaction with ion-
supported Ph3P B2
Phosphonium salt B2 (939 mg,1.5 mmol) was dried by a vacuum
pump for 2 h at 70 ꢀC. To the flask containing phosphonium salt B2
were added NaH (80 mg, 2.0 mmol) and toluene (5 mL). The
obtained mixture was stirred for 1 h at 0 ꢀC initially to room tem-
perature under an argon atmosphere. Then, 4-chlorobenzaldehyde
(141 mg, 1.0 mmol) was added to the solution at 0 ꢀC and the
obtained mixture was stirred for 9 h at 0 ꢀC initially to 60 ꢀC. After
the reaction, ether (10 mL) was added and the obtained mixture
was stirred for 10 min at room temperature. Then, the mixture was
filtered and washed with ether. Removal of the solvent from the
4.4.1. Phosphonium salt A1. Mp 174e178 ꢀC; IR (neat): 1721, 1492,
1297, 1144, 1113, 759, 723,690 cmꢁ1 1H NMR (400 MHz, CDCl3):
;
d
¼1.10 (t, J¼6.9 Hz, 3H), 3.43 (s, 9H), 4.08 (q, J¼6.9 Hz, 2H), 5.32 (d,
J¼13.8 Hz, 2H), 5.40 (s, 2H), 7.71e7.73 (m, 4H), 7.87e7.91 (m, 8H),
8.16e8.18 (m, 2H); 13C NMR (100 MHz, CDCl3):
d
¼14.12 (p), 30.43
filtrate
gave
1-(40-chlorophenyl)-2-(400-methylphenyl)ethene
(s), 52.56 (p), 62.93 (s), 66.44 (s), 118.10 (q), 118.81 (q), 120.63 (q),
121.33 (q), 130.62 (t), 130.72 (t), 134.37 (t), 134.45 (t) 134.63 (t),
134.70 (t), 134.74 (t), 134.78 (t), 165.15 (q); HRMS (ESI) calcd for
C26H32Br2NO2P [Mþ]: 579.0532. Found: 579.0506.
(E:Z¼75:25) in 90% purity, which was estimated by 1H NMR. Pure 1-
(40-chlorophenyl)-2-(400-methylphenyl)ethene was obtained in 91%
yield by short flash column chromatography on silica gel (CHCl3/
hexane¼10:1). The co-product, N-methyl-N-[4-(diphenylphos-
phono)benzyl]pyrrolidinium bromide, was recovered by the above
filtration in 98% yield.
4.4.2. Phosphonium salt A2. Mp 175e180 ꢀC; IR (neat): 3374, 1411,
1113, 822, 753, 741, 721, 691 cmꢁ1 1H NMR (400 MHz, CDCl3):
;
d
¼2.27 (s, 3H), 3.45 (s, 9H), 5.10 (d, J¼14.4 Hz, 2H), 5.44 (s, 2H),
7.64e7.72 (m, 8H), 7.77e7.84 (m, 4H), 8.22e8.24 (m, 2H); 13C NMR
(100 MHz, CDCl3):
4.7. Typical regeneration of ion-supported Ph3P A or B
d
¼21.21 (p), 28.47 (s), 52.56 (p), 66.50 (s), 117.85
Me2SO4 (1.1 mmol) was added to a flask containing 1-methyl-3-
(q), 118.52 (q), 120.34 (q), 121.01 (q), 129.85 (t), 130.60 (t), 130.70 (t),
131.35 (t), 131.39 (t), 134.58 (t), 134.70 (t), 134.77 (t), 134.97 (t),
[40-(diphenylphosphono)benzyl]pyrrolidinium
bromide
B
(1.0 mmol) in chloroform (6 mL) at 0 ꢀC. The obtained mixture was

956
N. Shimojuh et al. / Tetrahedron 67 (2011) 951e957
stirred for 24 h at 60 ꢀC under an argon atmosphere. After the re-
action, the mixture was concentrated by a vacuum pump. Then, 1,2-
dimethoxyethane (10 mL) and LiAlH4 (3.0 mmol) were added to the
reaction mixture at 0 ꢀC, and the obtained mixture was stirred for
2 h at room temperature under an argon atmosphere. The reaction
mixture was quenched with ice at first. Then, 1 N aq HBr (5 mL) was
added to the aqueous solution, and the obtained solution was
washed with ether twice. The aqueous solution was extracted with
CH2Cl2 (10 mLꢂ3), and the combined organic layer was dried over
Na2SO4. After removal of the solvent, 1-methyl-3-[40-(diphenyl-
phosphino)benzyl]pyrrolidinium bromide B was obtained in 95%
yield. Then, ethyl bromoacetate (334 mg, 2.0 mmol) or 4-methyl-
benzyl bromide (371 mg, 2.0 mmol) was added to a flask containing
(t, J¼7.1 Hz, 3H), 2.37 (s, 3H), 4.26 (q, J¼7.2 Hz, 2H), 6.39 (d, J¼16.0 Hz,
1H), 7.19 (d, J¼8.2 Hz, 2H), 7.42 (d, J¼8.2 Hz, 2H), 7.66 (d, J¼16.0 Hz,
1H); 13C NMR (100 MHz, CDCl3):
d¼14.33 (p), 21.44 (p), 60.39 (s),
117.15 (t), 128.02 (t), 129.59 (t), 131.71 (q), 140.60 (q), 144.57 (t), 167.19
(q); HRMS (ESI) calcd for C12H15O2 [MþH]þ: 191.1066. Found:
191.1066.
4.7.6. Ethyl (E)-3-(40-methoxyphenyl)-2-propenoate. Oil; IR (neat):
1711, 1634, 1604, 1254, 1171, 983 cmꢁ1; 1H NMR (400 MHz, CDCl3):
d
¼1.33 (t, J¼7.1 Hz, 3H), 3.84 (s, 3H), 4.25 (q, J¼7.3 Hz, 2H), 6.31 (d,
J¼16.0 Hz, 1H), 6.90 (d, J¼8.9 Hz, 2H), 7.48 (d, J¼8.9 Hz, 2H), 7.64 (d,
J¼16.0 Hz, 1H); 13C NMR (100 MHz, CDCl3):
¼14.34 (p), 55.36 (p),
d
60.31 (s), 114.29 (t), 115.73 (t), 127.18 (q), 129.66 (t), 144.23 (t),
161.30 (q), 167.33 (q); HRMS (ESI) calcd for C12H15O3 [MþH]þ:
207.1015. Found: 207.1017.
1-methyl-3-[40-(diphenylphosphino)benzyl]pyrrolidinium
bro-
mide B (441 mg, 1.0 mmol) in 1,2-dichloromethane (5 mL) at 0 ꢀC.
The obtained mixture was stirred for 24 h at 40 ꢀC under an argon
atmosphere. After the reaction, ether (10 mL) was added and the
obtained mixture was stirred for 30 min at 0 ꢀC. Then, the mixture
was filtered and washed with ether. Removal of the solvent from
the filtrate gave phosphonium salt B1 or B2 in 100% yield.
4.7.7. Ethyl (2E,4E)-5-phenyl-2,4-pentadienoate. Oil; IR (neat):
1706, 1626, 999, 756 cmꢁ1
;
1H NMR (400 MHz, CDCl3):
d
¼1.32 (t,
J¼7.1 Hz, 3H), 4.23 (q, J¼7.3 Hz, 2H), 5.99 (d, J¼15.1 Hz, 1H),
6.83e6.93 (m, 2H), 7.26e7.54 (m, 6H); 13C NMR (100 MHz, CDCl3):
d
¼14.32 (p), 60.33 (s), 121.32 (t), 126.23 (t), 127.16 (t), 128.79 (t),
4.7.1. Phosphonium salt B1. Mp 145e147 ꢀC; IR (Nujol): 3382, 2726,
129.00 (t), 136.02 (q), 140.34 (t), 144.52 (t), 167.05 (q); HRMS (ESI)
1720, 1586, 1305, 1155, 1109, 722, 687 cmꢁ1
;
1H NMR (400 MHz,
calcd for C13H15O2 [MþH]þ: 203.1066. Found: 203.1066.
CDCl3):
d
¼1.03 (t, J¼7.2 Hz, 3H), 2.08e2.20 (m, 2H), 2.22e2.36 (m,
2H), 3.23 (s, 3H), 3.70e3.80 (m, 2H), 3.98e4.10 (m, 4H), 5.41 (s, 2H),
4.7.8. Ethyl (E)-2-decenoate. Oil; IR (neat): 1724, 1655, 1265, 1189,
5.47 (d, J¼13.8 Hz, 2H), 7.65e7.98 (m, 12H), 8.14e8.22 (m, 2H); 13C
980 cmꢁ1; 1H NMR (400 MHz, CDCl3):
d¼0.88 (t, J¼6.9 Hz, 3H), 1.29
NMR (100 MHz, CDCl3):
d¼13.60 (p), 20.88 (s), 21.71 (s), 32.53 (s),
(t, J¼7.2 Hz, 11H), 1.39e1.51 (m, 2H), 2.19 (q, J¼7.6 Hz, 2H), 4.18 (q,
32.98 (s), 47.56 (p), 62.78 (s), 63.23 (s), 63.78 (s), 116.76 (q), 117.46
(q), 119.82 (q), 120.52 (q), 130.15 (t), 130.25 (t), 133.92 (t), 134.01 (t),
134.18 (t), 134.29 (t), 134.40 (t), 134.49 (t), 164.17 (q); HRMS (ESI)
calcd for C28H34Br2NO2P [Mþ]: 605.0669. Found: 605.0688.
J¼7.5 Hz, 2H), 5.81 (dt, J¼1.4, 16.3 Hz, 1H), 6.96 (dt, J¼7.0, 16.3 Hz,
1H); 13C NMR (100 MHz, CDCl3):
d¼14.01 (p), 14.23 (p), 22.58 (s),
27.98 (s), 29.01 (s), 29.06 (s), 31.69 (s), 32.15 (s), 60.05 (s), 121.18 (t),
149.42 (t), 166.75 (q); HRMS (ESI) calcd for C12H23O2 [MþH]þ:
199.1692. Found: 199.1690.
4.7.2. Phosphonium salt B2. Mp 135e137 ꢀC; IR (Nujol): 3408, 1601,
1587, 1514, 1439, 1112, 822, 743, 719, 691 cmꢁ1; 1H NMR (400 MHz,
4.7.9. Ethyl (E)-5-methyl-2,4-hexadienoate. Oil; IR (neat): 1713,
CDCl3):
d
¼2.02e2.18 (m, 2H), 2.22e2.38 (m, 2H), 2.26 (s, 3H), 3.23
1638, 1276, 1139, 992 cmꢁ1
;
1H NMR (400 MHz, CDCl3):
d
¼1.30 (t,
(s, 3H), 3.67e3.81 (m, 2H), 4.01e4.15 (m, 2H), 5.11 (d, J¼14.2 Hz,
J¼7.2 Hz, 3H),1.88 (s, 3H),1.90 (s, 3H), 4.20 (q, J¼6.8 Hz, 2H), 5.76 (d,
2H), 5.39 (s, 2H), 6.93 (s, 4H), 7.58e7.72 (m, 8H), 7.72e7.84 (m, 4H),
J¼15.2 Hz, 1H), 5.99 (d, J¼11.2 Hz, 1H), 7.56 (dd, J¼11.2, 15.2 Hz, 1H);
8.14e8.24 (m, 2H); 13C NMR (100 MHz, CDCl3):
d
¼20.36 (s), 20.42
13C NMR (100 MHz, CDCl3):
d
¼14.33 (p), 18.94 (p), 26.55 (p), 60.11
(p), 29.35 (s), 29.74 (s), 47.15 (p), 62.77 (s), 63.08 (s), 63.47 (s),115.95
(q), 116.63 (q), 119.12 (q), 119.79 (q), 128.81 (t), 129.45 (t), 129.55 (t),
129.63 (t), 129.74 (t), 130.41 (t), 132.32 (t), 132.41 (t), 133.70 (t),
134.45 (t), 135.36 (q), 137.64 (q); HRMS (ESI) calcd for C32H36Br2NP
[Mþ]: 623.0923. Found: 623.0958.
(s), 118.53 (t), 123.69 (t), 141.00 (t), 146.28 (q), 167.75 (q); HRMS
(ESI) calcd for C9H15O2 [MþH]þ: 155.1066. Found: 155.1067.
4.7.10. Ethyl (E)-4,4,4-trifluoro-3-phenylbut-2-enoate. Oil (lit.7); IR
(neat): 2986, 1736, 1655, 1446, 1028, 699 cmꢁ1; 1H NMR (400 MHz,
CDCl3):
d
¼1.04 (t, J¼7.2 Hz, 3H), 4.03 (q, J¼7.2 Hz, 2H), 6.60 (q,
4.7.3. Phosphonium salt B3. Mp 210e215 ꢀC; IR (Nujol): 3402,1602,
J¼1.4 Hz, 1H), 7.26e7.31 (m, 2H), 7.36e7.42 (m, 3H); 13C NMR
1586, 1458, 1439, 1219, 1112, 937, 752, 721, 659, 628 cmꢁ1; 1H NMR
(100 MHz, CDCl3):
d
¼13.64 (p), 61.03 (s), 122.49 (q), 124.54 (t),
(400 MHz, CDCl3):
d
¼0.85e0.95 (m, 3H), 1.15e1.25 (m, 2H),
128.13 (t), 128.60 (t), 129.26 (t), 131.02 (q), 142.29 (q), 164.11 (q); 19F
1.50e1.70 (m, 2H), 2.10e2.20 (m, 2H), 2.21e2.28 (m, 2H), 3.29 (s,
3H), 3.55e3.86 (m, 4H), 4.04e4.18 (m, 2H), 5.46 (s, 2H), 7.68e7.78
(m, 4H), 7.79e7.88 (m, 8H), 8.24e8.30 (m, 2H); 13C NMR (100 MHz,
NMR (400 MHz, CDCl3):
d¼ꢁ67.59; HRMS (ESI) calcd for C12H12F3O2
[MþH]þ: 245.0780. Found: 245.0784.
CDCl3):
d
¼13.64 (p), 21.03 (s), 22.60 (s), 22.99 (s), 23.70 (s), 23.83
4.7.11. (E)-1-Chloro-4-(40-methylstyryl)benzene. Mp 185e190 ꢀC
(lit.8 mp 200e204 ꢀC); IR (Nujol): 1511, 1488, 1092, 1014, 971, 824,
(s), 24.53 (s), 47.81 (p), 63.46 (s), 63.99 (s), 117.14 (q), 117.82 (q),
120.28 (q), 130.56 (t), 130.66 (t), 133.70 (t), 133.77 (t), 134.02 (t),
134.11 (t), 134.71 (t), 134.80 (t), 136.21 (q); HRMS (ESI) calcd for
C28H35Br2NP [MꢁH]þ: 574.0885. Found: 574.0879.
720 cmꢁ1
;
1H NMR (400 MHz, CDCl3):
d
¼2.36 (s, 3H), 6.99 (d,
J¼16.5 Hz, 1H), 7.06 (d, J¼16.5 Hz, 1H), 7.17 (d, J¼8.5 Hz, 2H), 7.31
(d, J¼9.0 Hz, 2H), 7.40 (d, J¼9.0 Hz, 2H), 7.42 (d, J¼8.5 Hz, 2H); 13C
NMR (100 MHz, CDCl3):
d
¼21.26 (p), 126.34 (t), 126.46 (t), 127.52
4.7.4. Ethyl (E)-3-(40-chlorophenyl)-2-propenoate. Oil; IR (neat):
(t), 128.78 (t), 129.23 (t), 129.43 (t), 132.89 (q), 134.19 (q), 136.02
(q), 137.80 (q); HRMS (APPI) calcd for C15H13Cl [Mþ]: 228.0700.
Found: 228.0698.
1714, 1638, 1269, 981 cmꢁ1
;
1H NMR (400 MHz, CDCl3):
d
¼1.34 (t,
J¼7.3 Hz, 3H), 4.27 (q, J¼7.1 Hz, 2H), 6.41 (d, J¼16.0 Hz, 1H), 7.36 (d,
J¼8.6 Hz, 2H), 7.45 (d, J¼8.6 Hz, 2H), 7.63 (d, J¼16.0 Hz, 1H); 13C
NMR (100 MHz, CDCl3):
d
¼14.29 (p), 60.61 (s), 118.85 (t), 129.15 (t),
4.7.12. (E)-1,2-Bis(40-methylphenyl)ethene. Mp 165e167 ꢀC (lit.8 mp
129.17 (t), 132.93 (q), 136.09 (q), 143.09 (t), 166.72 (q); HRMS (ESI)
180 ꢀC); IR (Nujol): 1515, 971, 822, 717 cmꢁ1 1H NMR (400 MHz,
;
calcd for C11H12O2Cl [MþH]þ: 211.0520. Found: 211.0524.
CDCl3):
d¼2.35 (s, 6H), 7.03 (s, 2H), 7.15 (d, J¼8.2 Hz, 4H), 7.39 (d,
J¼8.2 Hz, 4H); 13C NMR (100 MHz, CDCl3):
¼21.22 (p), 126.28 (t),
d
4.7.5. Ethyl (E)-3-(40-methylphenyl)-2-propenoate. Oil; IR (neat):
127.61 (t), 129.35 (t), 134.72 (q), 137.24 (q); HRMS (ESI) calcd for
1713, 1636, 1268, 1173, 984 cmꢁ1; 1H NMR (400 MHz, CDCl3):
d¼1.34
C16H17 [MþH]þ: 209.1325. Found: 209.1326.

N. Shimojuh et al. / Tetrahedron 67 (2011) 951e957
957
4.7.13. (E)-1-Methoxy-4-(40-methylstyryl)benzene. Mp 153e155 ꢀC
(lit.9 mp 160e162 ꢀC); IR (Nujol): 1605, 1515, 1253, 1177, 1031, 968,
4.7.17. (E)-1-(40-Methylphenyl)-2-phenyl-3,3,3-trifluoropropene. Oil
(lit.7); IR (neat): 3026, 1650, 1514, 1444, 1381, 1272, 1153, 1116,
824, 722 cmꢁ1
;
1H NMR (400 MHz, CDCl3):
d
¼2.34 (s, 3H), 3.81 (s,
703 cmꢁ1;1H NMR (400 MHz, CDCl3):
d
¼2.26 (s, 3H), 6.89 (d, J¼8.0 Hz,
2H), 6.96 (d, J¼8.0 Hz, 2H), 7.18 (s,1H), 7.28e7.36 (m, 2H), 7.37e7.42 (m,
3H); 13C NMR (100 MHz, CDCl3):
¼21.22 (p), 123.88 (q), 128.67 (t),
128.93 (t),128.99 (t),129.25 (q),129.90 (t),130.01 (t),130.66 (q),132.97
3H), 6.88 (d, J¼8.7 Hz, 2H), 6.94 (d, J¼16.7 Hz, 1H), 7.01 (d,
J¼16.7 Hz, 1H), 7.14 (d, J¼8.0 Hz, 2H), 7.38 (d, J¼8.0 Hz, 2H), 7.43 (d,
d
J¼8.7 Hz, 2H); 13C NMR (100 MHz, CDCl3):
¼21.19 (p), 55.27 (p),
d
114.08 (t), 126.13 (t), 126.52 (t), 127.18 (t), 127.55 (t), 129.33 (t),
130.30 (q), 134.83 (q), 137.01 (q), 159.10 (q); HRMS (ESI) calcd for
C16H17O [MþH]þ: 225.1274. Found: 225.1274.
(q),133.04(t),139.09 (q); 19F NMR (400 MHz, CDCl3):
d¼ꢁ65.59; HRMS
(ESI) calcd for C16H13F3 [Mþ]: 262.0964. Found: 262.0962.
4.7.18. (Z)-1-(4-Chlorophenyl)-1-pentene. Oil; IR (neat): 1652, 1491,
4.7.14. (E,E)-1-(40-Methylphenyl)-4-phenyl-1,3-butadiene. Mp 142e
145 ꢀC (lit.10 mp 152e153 ꢀC); IR (Nujol): 993, 973, 822, 804, 747, 720,
1092, 839 cmꢁ1; 1H NMR (400 MHz, CDCl3):
d
¼0.93 (t, J¼7.5 Hz, 3H),
1.43e1.50 (m, 2H), 2.26 (dq, J¼1.9, 7.4 Hz, 2H), 5.68 (td, J¼7.2,11.7 Hz,
690 cmꢁ1; 1H NMR (400 MHz, CDCl3):
d
¼2.35 (s, 3H), 6.62e6.71 (m,
1H), 6.35 (d, J¼11.7 Hz, 1H), 7.19 (d, J¼8.5 Hz, 2H), 7.28 (d, J¼8.5 Hz,
2H), 6.88e6.98 (m, 2H), 7.14 (d, J¼7.8 Hz, 2H), 7.22 (t, J¼8.9 Hz, 1H),
2H); 13C NMR (100 MHz, CDCl3):
127.69 (t), 128.22 (t), 130.00 (t), 132.09 (q), 133.71 (t), 136.21 (q);
HRMS (ESI) calcd for C11H13Cl [Mþ]: 262.0964. Found: 262.0962.
d
¼13.80 (p), 23.03 (s), 30.62 (s),
7.27e7.36 (m, 4H), 7.43 (d, J¼7.8 Hz, 2H); 13C NMR (100 MHz, CDCl3):
d
¼21.26 (p), 126.30 (t), 127.42 (t), 128.31 (t), 128.63 (t), 128.98 (t),
129.37 (t), 129.42 (t), 132.23 (t), 132.83 (t), 134.57 (q), 137.46 (q),
137.49 (q); HRMS (ESI) calcd for C17H17 [MþH]þ: 221.1325. Found:
221.1323.
References and notes
1. Fieser, L. F.; Fieser, M. 1967, 1, 1247; 1969, 2, 445; 1972, 3, 320; 1974, 4, 549;
1975, 5, 725; 1977, 6, 643; 1979, 7, 404; 1980, 8, 516; 1981, 9, 503; 1982, 10, 448;
1984, 11, 588; 1986, 12, 550; 1988, 13, 331; 1989, 14, 336; 1990, 15, 352; 1992, 16,
366; Reagents for Organic Synthesis, John Wiley: New York, NY.
2. Comprehensive Organic Transformations; Larock, R. C., Ed.; VCH: New York, NY,
1989; p 353 and 849.
3. (a) Wittig, G.; Schollkopf, U. Chem. Ber. 1954, 87, 1318; (b) Wittig, G.; Haag, W.
Chem. Ber. 1955, 88, 1654 Recent papers: (c) Cao, J.; Zhou, F.; Zhou, J. Angew.
Chem., Int. Ed. 2010, 49, 4976; (d) Sousa-Pedraes, A.; Vinas, C.; Teixidor, F. Chem.
Commun. 2010, 46, 2998; (e) Leung, P. S.; Teng, Y.; Toy, P. H. Synlett 2010, 1997;
(f) McNulty, J.; Das, P.; MeLeod, D. Chem.dEur. J. 2010, 16, 6756.
4. (a) Mizoroki, T.; Mori, K.; Ozaki, A. Bull. Chem. Soc. Jpn. 1971, 44, 581; (b) Heck,
R. F.; Nolley, J. P. J. Org. Chem. 1972, 37, 2320; (c) Sonogashira, K.; Tohda, Y.;
Hagihara, N. Tetrahedron Lett. 1975, 16, 4467; (d) Scott, W. J.; Crisp, G. T.; Stille, J.
K. J. Am. Chem. Soc. 1984, 106, 4630; (e) Stille, J. K. Pure Appl. Chem. 1985, 57,
1771; (f) Miyaura, N.; Yanagi, T.; Suzuki, A. Tetrahedron Lett. 1979, 3437; (g)
Suzuki, A. Acc. Chem. Res. 1982, 15, 178.
4.7.15. (E)-1-(40-Methylphenyl)-1-nonene. Oil; IR (neat): 1457,1038,
964, 792, 722 cmꢁ1; 1H NMR (400 MHz, CDCl3):
d
¼0.88 (t, J¼7.2 Hz,
3H), 1.20e1.38 (m, 8H), 1.40e1.48 (m, 2H), 2.18 (q, J¼7.5 Hz, 2H),
2.32 (s, 3H), 6.16 (dt, J¼6.9, 16.0 Hz,1H), 6.34 (d, J¼16.0 Hz,1H), 7.09
(d, J¼8.0 Hz, 2H), 7.23 (d, J¼8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3):
d
¼14.09 (p), 21.10 (p), 22.67 (s), 29.19 (s), 29.45 (s), 30.02 (s), 31.85
(s), 33.04 (s), 125.77 (t), 129.13 (t), 129.47 (t), 130.20 (t), 135.17 (q),
136.37 (q); HRMS (ESI) calcd for C16H25 [MþH]þ: 217.1951. Found:
217.1953.
4.7.16. (E,E)-4-Methyl-1-(40-methylphenyl)-1,3-pentadiene. Oil; IR
(neat): 3021, 2965, 2920, 1512, 971, 957, 822, 797 cmꢁ1 1H NMR
;
(400 MHz, CDCl3):
d
¼1.84 (s, 3H), 1.85 (s, 3H), 2.33 (s, 3H), 5.99 (d,
5. Imura, Y.; Shimojuh, N.; Togo, H. Tetrahedron 2010, 66, 3421.
6. Imamoto, T.; Kikuchi, S.; Miura, T.; Wada, Y. Org. Lett. 2001, 3, 87.
7. Konno, T.; Chae, J.; Tanaka, T.; Ishihara, T.; Yamanaka, H. J. Fluorine Chem. 2006,
127, 36.
8. Warner, P.; Sutherland, R. J. Org. Chem. 1992, 57, 6294.
9. Heynekamp, J. J.; Weber, W. M.; Hunsaker, L. A.; Gonzales, A. M.; Orlando, R. A.;
J¼10.6 Hz, 1H), 6.40 (d, J¼15.5 Hz, 1H), 6.94 (dd, J¼10.6, 15.5 Hz,
1H), 7.10 (d, J¼8.0 Hz, 2H), 7.29 (d, J¼8.0 Hz, 2H); 13C NMR
(100 MHz, CDCl3):
d
¼18.53 (p), 21.18 (p), 26.21 (p), 124.79 (t),
125.54 (t), 125.96 (t), 129.24 (t), 129.47 (t), 135.31 (q), 135.90 (q),
136.68 (q); HRMS (ESI) calcd for C13H17 [MþH]þ: 173.1325. Found:
173.1326.
Deck, L. M.; Jagt, D. L. V. J. Med. Chem. 2006, 49, 7182.
10. Kamigata, N.; Ozaki, J.; Kobayashi, M. Chem. Lett. 1985, 6, 705.