Nickel(II)-catalyzed carbon-carbon bond formation reaction of functionalized organozinc reagents with aromatic aldehydes

Article abstract of DOI:10.1016/j.tet.2008.09.066

In the presence of a silylating reagent and catalytic amount of Ni(acac)₂, organozinc halides reacted with aromatic aldehydes to give the corresponding dialkylation products in good to excellent yields under mild conditions.

Full text of DOI:10.1016/j.tet.2008.09.066

Tetrahedron 64 (2008) 11124–11128
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Nickel(II)-catalyzed carbon–carbon bond formation reaction of functionalized
organozinc reagents with aromatic aldehydes
,
b
,
a
a
Ying Fu a, Jin-Xian Wang a , Kehu Wang , Yulai Hu
*
a Institute of Chemistry, Department of Chemistry, Northwest Normal University, 967 Anning Road (E.), Lanzhou 730070, PR China
b State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730070, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 29 April 2008
Received in revised form 8 September 2008
Accepted 23 September 2008
Available online 30 September 2008
In the presence of a silylating reagent and catalytic amount of Ni(acac)2, organozinc halides reacted with
aromatic aldehydes to give the corresponding dialkylation products in good to excellent yields under
mild conditions.
Ó 2008 Published by Elsevier Ltd.
Keywords:
Aromatic aldehydes
Dialkylation
Nickel(II)-catalysis
Organozinc reagents
1. Introduction
that functional organozinc iodides RZnI could be transmetallated
into organozinccopper reagents RCu(CN)ZnI with THF soluble
Transition metal catalyzed carbon–carbon bond formation is
one of the most useful reactions in synthetic organic chemistry,
particularly in the synthesis of complex natural products with bi-
ological activity. Many methods1 have been described for the re-
actions of carbon–carbon bond formation. The reaction of
organozinc reagents with carbonyl compounds is also an important
carbon–carbon bond formation reaction in organic chemistry.2,3
Organozinc reagents are very useful and versatile organometallic
reagents in organic chemistry because of their high functional
group compatibility4 and excellent reactivity in the presence of an
appropriate transition metal catalyst.5
In 1978, Mukaiyama first reported that Et2Zn could add
smoothly to benzaldehyde in the presence of aminoalcochols.6
Since then, much attention has been devoted to the reaction,7 es-
pecially the enantioselective addition reaction8 of dialkylzinc
compounds with aldehydes and ketones. However, dialkylzinc
compounds are relatively stable and poorly reactive organometallic
compounds. Furthermore, in most cases only one of the two alkyl
groups is transferred, wasting 50% of the precious reagent.
Alkylzinc halides, RZnX, which carry only one alkyl side chain,
offer alternatives. However, these species are less reactive and often
necessitate the use of additional catalyst. In 1988, Knochel9 showed
copper salt CuCN$2LiCl, and then coupled with acyl chlorides or
conducted 1,4-additon reaction with enones. This report greatly
broadened the scope of organozinc reagents in organic synthesis.
Now these reagents have been successfully used in coupling re-
actions with organic halides, 1,2-addition reactions with aldehyde
or ketones, and 1,4-addition reactions with b-unsaturated carbonyl
compounds or nitro olefins.2,7,10 But in these cases, stoichiometric
CuCN$2LiCl must be used in most of these reactions. Recently,
Nickel-catalyzed coupling reaction of organic halides with organo-
zinc reagents has been reported.11,12 Addition of alkylzinc to
carbonyl compounds to synthesize optically active secondary al-
cohols have also been reported.8,13,14 We also reported15 the tran-
sition metal catalyzed carbon–carbon bond formation reaction of
functionalized organozinc reagents in the presence of a silylating
reagent. However, we have found very few literatures on the dia-
lkylation of aromatic aldehydes.16,17 In our earlier communication,18
we have showed Ni(II)-catalyzed dialkylation of aromatic alde-
hydes and organozinc reagents proceeded efficiently in the pres-
ence of a silylation reagent.
2. Results and discussion
We now report a novel carbon–carbon bond formation reaction
via Ni(acac)2-catalyzed dialkylation of aromatic aldehydes and
organozinc reagents. Nickel(II)-catalyzed dialkylation of benzalde-
hyde with n-C8H17ZnI, affording 1-octyl-1-phenylnonane, was
* Corresponding author. Tel.: þ86 931 7970567; fax: þ86 931 7768159.
E-mail address: wangjx@nwnu.edu.cn (J.-X. Wang).
0040-4020/$ – see front matter Ó 2008 Published by Elsevier Ltd.
doi:10.1016/j.tet.2008.09.066

Y. Fu et al. / Tetrahedron 64 (2008) 11124–11128
11125
Table 2
chosen as a model reaction to optimize the reaction conditions. The
results are summarized in Table 1.
Nickel(II)-catalyzed dialkylation reaction of aromatic aldehydes with functional
organozinc reagentsa
Among several catalysts screened, the best yield was obtained
when [Ni(acac)2] was employed (Table 1, entry 3). In the presence
of [PdCl2(PPh3)2], [CoCl2(PPh3)2], [CoCl(PPh3)3], [NiCl2(PPh3)2],
[Ni(OAc)2] or NiCl2, the reaction was unsuccessful (Table 1, entries
14–19). The amount of [Ni(acac)2] affected the yield and the use of
10 mol % of the catalyst gave the best results (entries 1–3). When A,
B or C was employed as a ligand in the presence of Me3SiCl and
10 mol % of [Ni(acac)2], the yields of the corresponding 1-octyl-1-
phenylnonane were 78, 76, and 82%, respectively (Table 1, entries
1–3). We have also investigated the effect of the reaction time and
the temperature on this reaction. It was found that the high yield of
1-octyl-1-phenylnonane was obtained from ꢀ18 ꢁC to room tem-
perature for 12 h (Table 1, entries 1–3, 12, and 13). In the absence of
[Ni(acac)2] or Me3SiCl, no product was formed. For example, no
product was isolated after the reaction of benzaldehyde with
n-C8H17ZnI without [Ni(acac)2] and chlorotrimethylsilane (Table 1,
entries 5 and 11).
FG-R'ZnI (2 equiv)
O
R'-FG
R'-FG
2
1) Ni(acac)2/Et3N, THF, 65 °C
H
2) Me3SiCl, THF, -18 °C to RT
1
R
3a-t
R
Entry
1
R
FG-R0
Productb
Yieldc (%)
H
n-C4H9
n-C4H9
n-C6H13
3a 74
3b 72
3c 82
2
3
4-MeO
H
MeO
( )3
( )3
( )3
In order to define the scope and the limitation of this new dia-
lkylation reaction, the reaction of various aldehydes and organozinc
reagents were examined as listed in Table 2.
4
5
6
4-MeO
n-C6H13
3d 79
3e 73
3f 85
( )3
MeO
MeO
As shown in Table 2, the reaction of substituted aromatic alde-
hydes with RZnI in the presence of the silylating reagent, a tertiary
amine, and catalytic amount of Ni(acac)2 from ꢀ18 ꢁC to room
temperature for 12 h gave the corresponding 1-alkyl-1-arylalkanes
3 in good to excellent yields (72–85%, Table 2, entries 1–12).
Methoxyl substituent at meta or para position of the aromatic ring
did not exert strong influence upon the dialkylation reaction, while
the ortho substituted compound gave the dialkylated product in 50%
yield18 (Table 2, entries 2, 4, 5, 6, 9,10, 12, 13, 16, and 17). Amazingly,
( )3
( )3
3,4-(MeO)2 n-C6H13
MeO
( )5
( )5
4-MeO
n-C8H17
MeO
( )5
7
8
H
H
n-C8H17
n-C7H15
3g 83
3h 81
( )5
Table 1
( )4
( )4
Effects of the type and the amount of catalysts, the type of Lewis acid, and reaction
conditions on the formation of 3ga
O
n-C8H17ZnI (2equiv.)
( )4
Nickel(II)/L, THF
H
9
4-MeO
n-C7H15
3i 77
Lewis acid, THF
( )4
3g
MeO
MeO
( )4
( )4
10
11
12
3,4-(MeO)2 n-C7H15
3j 69
3k 82
3l 78
B =
C = NEt3
L: A =
CH2N
CH2N
CH2NEt2
CH2NEt2
MeO
( )6
( )6
Entry
Catalyst (mol %)
L
Lewis acid
Conditions
Yieldb (%)
H
n-C9H19
n-C9H19
1
2
3
4
5
6
7
8
Ni(acac)2 (10)
Ni(acac)2 (10)
Ni(acac)2 (10)
Ni(acac)2 (5)
d
A
B
C
C
C
C
C
C
C
d
C
C
C
(CH3)3SiCl
(CH3)3SiCl
(CH3)3SiCl
(CH3)3SiCl
(CH3)3SiCl
AlCl3
BF3$OEt2
(CH3)3SiCl
(CH3)3SiCl
(CH3)3SiCl
d
ꢀ18 ꢁC/rt, 12 h
ꢀ18 ꢁC/rt, 12 h
ꢀ18 ꢁC/rt, 12 h
ꢀ18 ꢁC/rt, 12 h
ꢀ18 ꢁC/rt, 12 h
ꢀ18 ꢁC/rt, 12 h
ꢀ18 ꢁC/rt, 12 h
ꢀ18 ꢁC/rt, 12 h
ꢀ18 ꢁC/rt, 12 h
ꢀ18 ꢁC/rt, 12 h
ꢀ18 ꢁC/rt, 12 h
0 ꢁC, 12 h
78
76
82
31
0
( )6
( )6
4-MeO
MeO
Ni(acac)2 (10)
Ni(acac)2 (10)
Ni(acac)2 (10)
Ni(acac)2 (0.6)
Ni(acac)2 (10)
Ni(acac)2 (10)
Ni(acac)2 (10)
Ni(acac)2(10)
[PdCl2(PPh3)2] (2)
[NiCl2(PPh3)2] (10)
[CoCl2(PPh3)2] (10)
[CoCl(PPh3)3] (10)
Ni(OAc)2(10)
NiCl2(10)
0
0
60
42
18
0
28
24
0c
0c
0c
0c
0
13
4-MeO
3m 74
9
10
11
12
13
14
15
16
17
18
19
MeO
(CH3)3SiCl
(CH3)3SiCl
(CH3)3SiCl
(CH3)3SiCl
(CH3)3SiCl
(CH3)3SiCl
(CH3)3SiCl
(CH3)3SiCl
rt, 12 h
14
15
16
H
3n 79
3o 77
3p 78
ꢀ18 ꢁC/rt, 12 h
ꢀ18 ꢁC/rt, 12 h
ꢀ18 ꢁC/rt, 12 h
ꢀ18 ꢁC/rt, 12 h
ꢀ18 ꢁC/rt, 12 h
ꢀ18 ꢁC/rt, 12 h
Cl
Cl
C
C
H
Cl
Cl
0
a
All reactions were carried out using 12 mmol of benzaldehyde with 25 mmol of
n-C8H17ZnI, 24 mmol of Lewis acid, and 4.8 mmol of L (2.4 mmol for A or B, 4.8 mmol
for C) in 20 mL of THF.
Cl
Cl
4-MeO
b
Isolated yield.
The major product was E-alkene.
c
MeO
(continued on next page)

11126
Y. Fu et al. / Tetrahedron 64 (2008) 11124–11128
atmosphere was heated to 65 ꢁC for 2–3 min and then cooled to
Table 2 (continued )
room temperature. Then chlorotrimethylsilane (0.2 mL) was added
and the mixture was stirred at room temperature for 20 min. A
solution of RI (25 mmol) in THF (10 mL) was added dropwise and
the mixture was stirred for 12 h at 35–40 ꢁC. The resulting solution
of RZnI in THF was ready to use. In another three-neck flask,
Ni(acac)2 (1.2 mmol), Et3N (0.48 g, 4.8 mmol), and THF (10 mL)
were added and heated at 60 ꢁC under argon for 10 min. After
cooling to room temperature, the solution of RZnI in THF obtained
above was added and the resulting mixture was cooled to ꢀ18 ꢁC. A
solution of aromatic aldehyde (12 mmol), chlorotrimethylsilane
(24 mmol), and THF (10 mL) was added drop by drop and the
temperature was allowed to rise to room temperature. After the
reaction mixture was stirred for 12 h, saturated NH4Cl in water
solution (10 mL) and Et2O (10 mL) were added, and the mixture was
stirred for 10 min. The organic layer was separated, dried over
anhydrous MgSO4, and concentrated. Purification of the crude re-
action mixture by chromatography on a silica gel column using
petroleum/diethyl ether as the eluent gave the pure product. All
compounds were characterized by IR, 1H NMR, 13C NMR, micro-
analyses, and mass spectroscopy.
Entry
R
FG-R0
Productb
Yieldc (%)
Cl
Cl
MeO
MeO
17
3,4-(MeO)2
3q 67
Cl
Br
Br
Br
18
19
H
H
3r 78
3s 63
COOEt
COOEt
CO2Et
( )2
20
2-MeO
n-C5H11
3t 50
( )2
OMe
a
All reaction were conducted on the scale of 12 mmol of aldehydes with 25 mmol
of organozinc reagents, 1.2 mmol of Ni(acac)2, 24 mmol of Me3SiCl, and 4.8 mmol of
Et3N in 20 mL of THF.
b
All products were characterized by IR, 1H NMR, 13C NMR, and MS.
Isolated yield.
c
4.2.1. 1-Butyl-1-phenylpentane 3a
1
Oil; H NMR (400 MHz, CDCl3, 25 ꢁC, TMS):
d¼7.34 (t, J¼7.2 Hz,
we also found that these reactions tolerated various RZnI. The
structure of alkyl group of RZnI has little effects on the yields
(Table 2, entries 1, 3, 7, 8, 11, and 14). Under the same conditions,
functionalized alkylzinc iodides gave the products in good yields
(Table 2, entries 15–19). Functional groups such as chloro, bromo,
and ester groups were introduced to the corresponding dialkylation
products (Table 2, entries 17–19).
2H, Ar–H), 7.23 (d, J¼7.2 Hz, 1H), 7.20 (d, J¼7.6 Hz, 2H), 2.55–2.50
(m, 1H), 1.72–1.62 (m, 2H), 1.60–1.58 (m, 2H), 1.34–1.28 (m, 4H),
1.22–1.16 (m, 4H), 0.89 (t, J¼7.2 Hz, 6H); 13C NMR (100 MHz, CDCl3,
25 ꢁC):
d
¼146.4, 128.1, 127.6, 125.7, 46.0, 36.7, 29.8, 22.8, 14.0; DEPT
(100 MHz, CDCl3, 25 ꢁC):
29.8, 22.8, 14.0; IR (neat):
d
¼146.4, 128.1, 127.6, 125.7, 46.0, 36.7,
~
n
¼3027, 2958, 2926, 2858, 1465, 1378,
758, 700 cmꢀ1; MS (70 eV, EI): m/z (%): 204 (3.7) [Mþ], 147 (20.1),
117 (2.8), 91 (100), 77 (5). Anal. Calcd (%) for C15H24 (204.4): C,
88.16; H, 11.84. Found: C, 88.05; H, 11.97.
3. Conclusion
In conclusion, a novel, general, and efficient method of the
[Ni(acac)2]-catalyzed dialkylation of aromatic aldehydes with
functionalized organozinc halides in the presence of a silylation
reagent has been developed. The generality and synthetic useful-
ness of this method has been demonstrated in the efficient syn-
thesis of the polyfunctionalized 1-alkyl-1-arylalkanes. This reaction
uses more easily available organozinc halides rather than dia-
lkylzinc reagents, gives higher yields of the products, tolerates
multiple functional groups, and provides a new method to form
dialkylated products from aldehydes.
4.2.2. 1-Butyl-1-(4-methoxyphenyl)pentane 3b
1
Oil; H NMR (200 MHz, CDCl3, 25 ꢁC, TMS):
d
¼7.04 (dt, J¼6.4,
2.0 Hz, 2H), 6.83 (dt, J¼6.4, 2.0 Hz, 2H), 3.78 (s, 3H), 2.44–2.38 (m,
1H), 1.62–1.49 (m, 4H), 1.20 (br s, 8H), 0.83 (t, J¼7.2 Hz, 6H); 13C
NMR (50 MHz, CDCl3, 25 ꢁC):
d
¼157.6, 138.5, 128.4, 113.5, 55.1, 45.1,
~
36.9, 29.8, 22.8, 14.0; IR (neat):
n
¼2925, 2856, 1608, 1592, 1464,
1375, 1261, 1032, 765, 692 cmꢀ1; MS (70 eV, EI): m/z (%): 234 (8)
[ Mþ], 177 (55), 121 (100), 91 (4), 77 (2). Anal. Calcd (%) for C16H26
(234.4): C, 81.99; H, 11.18. Found: C, 81.92; H, 11.13.
O
4. Experimental
4.2.3. 1-Hexyl-1-phenylheptane 3c
Oil; 1H NMR (400 MHz, CDCl3, 25 ꢁC, TMS):
d
¼7.29 (q, J¼7.2 Hz,
4.1. General remarks
2H), 7.20 (d, J¼7.2 Hz, 1H), 7.16 (d, J¼7.6 Hz, 2H), 2.51–2.47 (m, 1H),
1.67–1.58 (m, 2H), 1.57–1.54 (m, 2H), 1.24 (br s, 12H), 1.17–1.12 (m,
1H NMR spectra were recorded on a Brucker AM 400 MHz and
Brucker AC-E 200 MHz spectrometers in CDCl3 with TMS as an
internal standard. 13C NMR spectra were obtained on a Brucker
AM-400 operating at 100 MHz or a Brucker AC-E 200 operating at
50 MHz. IR spectra were recorded on an Alpha Centauri FT-IR
spectrometer. Mass spectra were recorded on a HP 5988A and GC/
MS/DS instruments. Elemental analyses were carried out on Carlo
Erba-1106 instruments. Purification of products was performed via
flash chromatography with 200–400 mesh silica gel (10:1 petro-
leum/diethyl ether). All substrates and reagents were obtained
commercially except RZnX and Ni(acac)2, which were prepared
by standard procedures. THF was distilled from sodium/
benzophenone.
4H), 0.88 (t, J¼6.4 Hz, 6H); C NMR (100 MHz, CDCl3, 25 ꢁC):
13
d
¼146.4, 128.1, 127.6, 125.6, 46.1, 37.0, 31.8, 29.5, 27.6, 22.7, 14.1; IR
~
n
(neat):
¼3063, 3027, 2950, 2927, 2858, 1603, 1493, 1453, 1370,
1069, 759, 700 cmꢀ1; MS (70 eV, EI): m/z (%): 262 (26) [Mþþ2], 176
(43), 134 (6), 120 (17), 92 (100). Anal. Calcd (%) for C19H32 (260.5): C,
87.62; H, 12.38. Found: C, 87.80; H, 12.38.
4.2.4. 1-Hexyl-1-(4-methoxyphenyl)heptane 3d
1
Oil; H NMR (400 MHz, CDCl3, 25 ꢁC, TMS):
d¼7.06 (dd, J¼7.6,
2.0 Hz, 2H), 6.85 (dd, J¼7.6, 2.0 Hz, 2H), 3.81 (s, 3H), 2.44–2.41 (m,
1H), 1.65–1.57 (m, 2H), 1.55–1.49 (m, 2H), 1.23 (br s, 12H), 1.22–
1.07 (m, 4H), 0.87 (t, J¼6.8 Hz, 6H); 13C NMR (100 MHz, CDCl3,
25 ꢁC):
22.7, 14.1; IR (neat):
d
¼157.5, 138.5, 128.4, 113.5, 55.1, 45.2, 37.2, 31.8, 29.4, 27.6,
~
n
¼2924, 2854, 1611, 1578, 1510, 1461, 1374,
4.2. Typical experimental procedure for the synthesis of 3a–t
1300, 1247, 1176, 1106, 1040, 828, 724, 673, 574 cmꢀ1; MS (70 eV,
EI): m/z (%): 292 (20) [Mþþ2], 207 (74), 122 (100), 92 (4), 78 (2).
Anal. Calcd (%) for C20H34O (290.5): C, 82.69; H, 11.80. Found: C,
82.59; H, 11.68.
A mixture of zinc dust (1.7 g, 26 mmol), 1,2-dibromoethane
(0.2 mL), and THF (2 mL) in a dry three-neck flask under argon

Y. Fu et al. / Tetrahedron 64 (2008) 11124–11128
11127
4.2.5. 1-Hexyl-1-(3,4-dimethoxyphenyl)heptane 3e
Oil; 1H NMR (400 MHz, CDCl3, 25 ꢁC, TMS):
1H), 1.63–1.54 (m, 2H), 1.53–1.48 (m, 2H), 1.27–1.11 (m, 20H), 0.86
d
¼6.79 (d, J¼7.6 Hz,
(t, J¼7.2 Hz, 6H); 13C NMR (100 MHz, CDCl3, 25 ꢁC):
¼148.6, 146.9,
d
1H), 6.67 (dd, J¼8.8, 1.2 Hz, 2H), 3.88 (s, 3H), 3.87 (s, 3H), 2.43–2.37
139.0, 119.5, 110.9, 110.6, 55.7, 45.6, 37.1, 31.9, 29.7, 29.2, 27.6, 22.6,
~
(m,1H),1.64–1.53 (m, 2H),1.52–1.47 (m, 2H),1.24 (br s,16H), 0.85 (t,
14.1; IR (neat):
n
¼2928, 2856, 1606, 1594, 1515, 1464, 1410, 1362,
13
J¼6.9 Hz, 6H); C NMR (100 MHz, CDCl3, 25 ꢁC):
d¼148.6, 146.8,
1261, 1235, 1156, 1140, 1088, 1032, 867, 842, 809, 754 cmꢀ1; MS
(70 eV, EI): m/z (%): 348 (0.03) [Mþ], 318 (0.08), 249 (2.7), 219
(12.7), 179 (2.3), 167 (56.2), 151 (33.2), 147 (2.8), 139 (38.1), 134
(32.6), 121 (100), 108 (6.4), 91 (11.7), 77 (14.6), 41 (62.8). Anal. Calcd
(%) for C23H40O2 (348.3): C, 79.25; H, 11.57. Found: C, 79.30; H, 11.62.
139.0, 119.5, 110.8, 110.5, 55.7, 45.6, 37.0, 31.7, 29.4, 27.5, 22.6, 14.0;
DEPT (100 MHz, CDCl3, 25 ꢁC):
110.5, 55.7, 45.6, 37.0, 31.7, 29.4, 27.5, 22.6, 14.0; IR (neat):
d
¼148.6, 146.8, 139.0, 119.5, 110.8,
~
n
¼2996,
2927, 2855, 1605, 1592, 1515, 1464, 1410, 1376, 1325, 1261, 1235,
1150, 1143, 1031, 852, 806, 764, 692, 652 cmꢀ1; MS (70 eV, EI): m/z
(%): 321 (2) [Mþþ1], 320 (9) [Mþ], 235 (22), 151 (100), 91 (12), 77
(4), 57 (2), 43 (9). Anal. Calcd (%) for C21H36O2 (320.5): C, 78.69; H,
11.32. Found: C, 78.66; H, 11.26.
4.2.11. 1-Honyl-1-phenyldecane 3k
1
Oil; H NMR (400 MHz, CDCl3, 25 ꢁC, TMS)
d
¼7.31 (t, J¼7.2 Hz,
2H), 7.21 (d, J¼7.2 Hz, 1H), 7.16 (d, J¼7.2 Hz, 2H), 2.51–2.48 (m, 1H),
1.69–1.61 (m, 2H),1.59–1.55(m, 2H),1.25(brs, 28H), 0.91 (t, J¼6.4 Hz,
4.2.6. 1-Octyl-1-(4-methoxyphenyl)nonane 3f
6H); 13C NMR (100 MHz, CDCl3, 25 ꢁC):
d¼146.4, 128.1, 127.6, 125.6,
Oil; 1H NMR (400 MHz, CDCl3, 25 ꢁC, TMS):
d¼7.08 (d, J¼8.8 Hz,
46.1, 37.0, 31.9, 29.8, 29.7, 29.6, 29.4, 27.6, 22.7,14.1;IR(neat):
n
¼3062,
~
2H), 6.85 (d, J¼8.8 Hz, 2H), 3.82 (s, 3H), 2.51–2.25 (m, 1H), 1.64–1.56
(m, 2H),1.52–1.48 (m, 2H),1.30–1.12 (m, 24H), 0.90 (t, J¼6.4 Hz, 6H);
3027, 2926, 2854, 1603, 1493, 1465, 1378, 1074, 760, 722, 700 cmꢀ1
;
MS(70 eV, EI):m/z(%):345(0.1)[Mþþ1], 344(0.5)[Mþ], 217 (20),147
(10), 133 (13), 119 (16), 91 (100), 77 (2), 43 (41). Anal. Calcd (%) for
C25H44 (344.6): C, 87.13; H, 12.87. Found: C, 87.24; H, 12.70.
13C NMR (100 MHz, CDCl3, 25 ꢁC):
45.1, 37.1, 31.9, 29.8, 29.5, 29.3, 27.6, 22.7, 14.1; IR (neat):
d
¼157.5, 138.5, 128.4, 113.5, 55.1,
~
n
¼2926,
2854, 1611, 1504, 1511, 1464, 1377, 1247, 1177, 1041, 820 cmꢀ1; MS
(70 eV, EI): m/z (%): 346 (11.6) [Mþ], 203 (52), 161 (0.4), 147 (10.6),
133 (13.5), 119 (18), 105 (21), 91 (100), 57 (7.3). Anal. Calcd (%) for
C24H42O (346.6): C, 83.17; H, 12.21. Found: C, 83.07; H, 12.16.
4.2.12. 1-Honyl-1-(4-methoxyphenyl)decane 3l
Oil; 1H NMR (400 MHz, CDCl3, 25 ꢁC, TMS):
d
¼7.06 (d, J¼8.4 Hz,
2H), 6.84 (d, J¼8.4 Hz, 2H), 3.81 (s, 3H), 2.51–2.25 (m, 1H), 1.64–1.56
(m, 2H), 1.52–1.48 (m, 2H), 1.30–1.12 (m, 28H), 0.90 (t, J¼6.8 Hz,
4.2.7. 1-Octyl-1-phenylnonane 3g
6H); 13C NMR (100 MHz, CDCl3, 25 ꢁC):
55.1, 45.1, 37.1, 31.9, 29.8, 29.7, 29.6, 29.4, 27.6, 22.7, 14.1; IR (neat):
d
¼157.5, 138.5, 128.4, 113.5,
1
Oil; H NMR (400 MHz, CDCl3, 25 ꢁC, TMS):
d
¼7.34 (t, J¼7.2 Hz,
~
2H), 7.23 (d, J¼7.2 Hz, 1H), 7.17 (d, J¼7.2 Hz, 2H), 2.53–2.48 (m, 1H),
n
¼3028, 2925, 2854, 1611, 1582, 1511, 1462, 1349, 1246, 1174, 1097,
1.68–1.59 (m, 2H), 1.58–1.54 (m, 2H), 1.26 (br s, 20H), 1.19–1.13 (m,
1040, 832, 723 cmꢀ1; MS (70 eV, EI): m/z (%): 374 (3.9) [Mþ], 247
(14.8), 147 (4.7), 121 (100), 91 (4.8), 77 (1.5), 57 (47.8), 43 (7.8), 41
(11.3). Anal. Calcd (%) for C26H46O (374.6): C, 83.35; H, 12.38. Found:
C, 83.44; H, 12.29.
13
4H), 0.91 (t, J¼6.8 Hz, 6H); C NMR (100 MHz, CDCl3, 25 ꢁC):
d
¼146.4, 128.1, 127.7, 125.6, 46.0, 37.0, 31.9, 29.8, 29.5, 29.3, 27.6,
22.7, 14.1; DEPT (100 MHz, CDCl3, 25 ꢁC):
d¼146.4, 128.1, 127.7,
125.6, 46.0, 37.0, 31.9, 29.8, 29.5, 29.3, 27.6, 22.7, 14.1; IR (neat):
~
n
¼3062, 3027, 2956, 2926, 2855, 1937, 1865, 1603, 1493, 1465, 1377,
4.2.13. 2,2,4,10,12,12-Hexamethyl-7-(4-methoxyphenyl)-
tridecane 3m
1204, 1170, 1110, 1029, 905, 760, 700 cmꢀ1; MS (70 eV, EI): m/z (%):
316 (5.2) [Mþ], 233 (54), 121 (100), 91 (2), 77 (0.4). Anal. Calcd (%)
for C23H40 (316.6): C, 87.26; H, 12.74. Found: C, 87.26; H, 12.71.
Oil; 1H NMR (400 MHz, CDCl3, 25 ꢁC, TMS):
d
¼7.06 (d, J¼8.4 Hz,
2H), 6.84 (d, J¼8.4 Hz, 2H), 3.81 (s, 3H), 2.38–2.33 (m, 1H), 1.67–1.55
(m, 2H), 1.55–1.49 (m, 2H), 1.49–1.35 (m, 2H), 1.18–1.12 (m, 4H),
1.09–1.05 (m, 2H), 1.05–0.92 (m, 2H), 0.85 (br s, 24H); 13C NMR
4.2.8. 1-Heptyl-1-phenyloctane 3h
1
Oil; H NMR (400 MHz, CDCl3, 25 ꢁC, TMS):
d¼7.31 (q, J¼7.2 Hz,
(100 MHz, CDCl3, 25 ꢁC):
45.8, 45.6, 37.3, 34.8, 34.5, 31.0, 30.0, 29.4, 29.2, 22.8, 22.5; IR (neat):
d
¼157.5,138.5, 128.4, 113.5, 55.1, 51.3, 50.9,
2H), 7.21 (d, J¼7.2 Hz, 1H), 7.17 (d, J¼7.2 Hz, 2H), 2.53–2.47 (m, 1H),
~
1.70–1.61(m, 2H),1.59–1.54(m, 2H),1.25(brs,16H),1.17–1.10(m, 4H),
n
¼3100, 2953, 2715, 1612, 1584, 1512, 1466, 1392, 1376, 1364, 1301,
13
0.90 (t, J¼6.4 Hz, 6H); C NMR (100 MHz, CDCl3, 25 ꢁC):
d¼146.4,
1240, 1199, 1177, 1042, 959, 829, 808, 707, 605 cmꢀ1; MS (70 eV, EI):
m/z (%): 374 (0.1) [Mþ], 248 (0.5), 197 (0.6), 147 (30.9), 134 (7.4), 121
(17.6), 91 (8), 77 (3.9), 71 (100), 57 (5.6), 43 (20.3). Anal. Calcd (%) for
C26H46O (374.6): C, 83.35; H, 12.38. Found: C, 83.48; H, 12.19.
128.1, 127.7,125.7, 46.1, 37.0, 31.7, 29.8, 29.3, 27.7, 22.7,14.1; IR (neat):
~
n
¼3062, 3027, 2957, 2926, 2855, 1938, 1603, 1493, 1464, 1370, 1210,
1171, 1073, 759, 700 cmꢀ1; MS (70 eV, EI): m/z (%): 290 (21) [Mþþ2],
191 (48),148 (6),134 (13),106 (34), 91 (100), 78 (3). Anal. Calcd (%) for
C21H36 (288.3): C, 87.42; H, 12.58. Found: C, 87.36; H, 12.43.
4.2.14. 2,2,4,10,12,12-Hexamethyl-7-phenyltridecane 3n
1
Oil; H NMR (400 MHz, CDCl3, 25 ꢁC, TMS):
d
¼7.32 (dd, J¼7.6,
4.2.9. 1-Heptyl-1-(4-methoxyphenyl)octane 3i
7.2 Hz, 2H), 7.22 (d, J¼7.2 Hz, 1H), 7.18 (d, J¼8.0 Hz, 2H), 2.47–2.41
1
Oil; H NMR (400 MHz, CDCl3, 25 ꢁC, TMS):
d¼7.06 (dd, J¼8.4,
(m, 1H), 1.72–1.59 (m, 4H), 1.50–1.34 (m, 2H), 1.26–1.01 (m, 8H),
13
1.2 Hz, 2H), 6.84 (dt, J¼8.4, 2.0 Hz, 2H), 3.81 (s, 3H), 2.45–2.40 (m,
1.03–0.86 (m, 24H); C NMR (100 MHz, CDCl3, 25 ꢁC):
d¼146.4,
1H), 1.63–1.58 (m, 2H), 1.57–1.48 (m, 2H), 1.24 (br s, 16H), 1.16–1.10
128.1, 127.6, 125.7, 51.3, 50.9, 46.5, 37.3, 34.7, 34.3, 31.0, 30.0, 29.4,
29.4, 22.8, 22.5; DEPT (100 MHz, CDCl3, 25 ꢁC):
13
(m, 4H), 0.87 (t, J¼7.2 Hz, 6H); C NMR (100 MHz, CDCl3, 25 ꢁC):
d
¼146.4 (C), 128.1
d
¼157.5,138.5,128.4,113.4, 55.1, 45.1, 37.1, 31.9, 29.7, 29.2, 27.6, 22.6,
(CH), 127.6 (CH), 125.7 (CH), 51.3 (CH2), 50.9 (CH2), 46.5 (CH), 37.3
14.1; DEPT (100 MHz, CDCl3, 25 ꢁC):
d
¼157.5, 138.5, 128.4, 113.4,
(CH2), 34.7 (CH2), 34.3 (CH2), 31.0 (C), 30.0 (CH3), 29.4 (CH), 29.4
~
~
55.1, 45.1, 37.1, 31.9, 29.7, 29.2, 27.6, 22.6, 14.1; IR (neat):
n
¼2928,
(CH), 22.8 (CH3), 22.5 (CH3); IR (neat):
n
¼3062, 3027, 2945, 2716,
2857, 1608, 1597, 1515, 1468, 1265, 1235, 1140, 1000, 867, 842, 812,
758 cmꢀ1; MS (70 eV, EI): m/z (%): 320 (0.1) [Mþþ2], 319 (0.7)
[Mþþ1], 318 (3.1) [Mþ], 220 (5.0), 219 (31), 147 (2.6), 134 (3.7), 121
1602, 1492, 1467, 1393, 1377, 1364, 1247, 1203, 1170, 1070, 964, 846,
756, 700 cmꢀ1; MS (70 eV, EI): m/z (%): 345 (1) [Mþþ1], 344 (4)
[Mþ], 217 (4), 161 (19), 147 (12), 133 (6), 119 (12), 105 (24), 91 (44),
77 (2), 71 (10), 57 (100), 43 (24). Anal. Calcd (%) for C25H44 (344.6):
C, 87.13; H, 12.87. Found: C, 87.31; H, 12.74.
(100), 91 (5.1), 77 (2.6), 43 (13.2). Anal. Calcd (%) for C22H38
(318.5): C, 82.95; H, 12.02. Found: C, 82.76; H, 11.87.
O
4.2.10. 1-Heptyl-1-(3,4-dimethoxyphenyl)octane 3j
4.2.15. 5-Phenyl-1,9-dichlorononane 3o
Oil; 1H NMR (400 MHz, CDCl3, 25 ꢁC, TMS):
d
¼6.80 (d, J¼8.0 Hz,
Oil; 1H NMR (200 MHz, CDCl3, 25 ꢁC, TMS):
d
¼7.36–7.10 (m, 5H),
1H), 6.68 (d, J¼8.0 Hz, 2H), 3.88 (s, 3H), 3.86 (s, 3H), 2.43–2.37 (m,
3.62–3.41 (m, 4H), 2.37 (q, J¼6.8 Hz, 1H), 2.01–1.88 (m, 4H),

11128
Y. Fu et al. / Tetrahedron 64 (2008) 11124–11128
1.80–1.57 (m, 4H), 1.43–1.25 (m, 4H); 13C NMR (50 MHz, CDCl3,
(0.8) [Mþþ1], 262 (5) [Mþ], 121 (100), 91 (8), 77 (3). Anal. Calcd (%)
25 ꢁC):
(neat):
d
¼146.4, 128.1, 127.6, 125.7, 45.9, 31.8, 29.5, 27.6, 22.7; IR
for C18H30O (262.2): C, 82.38; H, 11.52. Found: C, 82.30; H, 11.61.
~
n
¼3080, 3058, 3025, 2955, 2930, 2848, 1663, 1598, 1493,
1444, 1383, 1305, 1274, 1070, 960, 741, 692 cmꢀ1; MS (70 eV, EI):
m/z (%): 272 (1.2) [Mþ], 183 (2.1), 155 (2.5), 145 (12.4), 117 (39.8), 92
(45), 105 (16.8), 91 (100), 77 (18.8). Anal. Calcd (%) for C15H22Cl2
(273.2): C, 65.93; H, 8.12. Found: C, 65.79; H, 7.86.
Acknowledgements
The work was supported by the Natural Science Foundation of
China (Grant 20272047, 20572086), the Gansu Natural Science
Foundation of China (0308RJZA-100), and Key Laboratory of Eco-
Environment-Related Polymer Material (Northwest Normal Uni-
versity), Ministry of the Education of China.
4.2.16. 5-(4-Methoxyphenyl)-1,9-dichlorononane 3p
Oil; 1H NMR (200 MHz, CDCl3, 25 ꢁC):
d
¼7.28–6.80 (m, 4H), 3.77
(s, 3H), 3.59–3.40 (m, 4H), 2.33 (q, J¼7.2 Hz,1H),1.95–1.23 (m, 12H);
13C NMR (50 MHz, CDCl3, 25 ꢁC):
44.6, 44.6, 35.0, 32.4, 30.0, 24.6; IR (neat):
d
¼157.8, 138.5, 128.4, 113.5, 55.6,
References and notes
~
n
¼2999, 2934, 2861,
2830,1609,1580, 1512, 1462, 1443, 1302,1240, 1176,1100,1036, 960,
833, 808, 754, 725 cmꢀ1; MS (70 eV, EI): m/z (%): 302 (2) [Mþ], 211
(45), 193 (17), 147 (5), 121 (100), 91 (31), 77 (4). Anal. Calcd (%) for
C16H24Cl2O (303.3): C, 63.37; H, 7.98. Found: C, 63.58; H, 8.16.
1. (a) Modern Organonickel Chemistry; Tamaru, Y., Ed.; Wiley-VCH: Weinheim,
2005; (b) Tsuji, J. Transition Metal Reagents and Catalysts: Inonovations in Organic
Synthesis; John Wiley and Sons: Chichester, UK, 2003; (c) Godleski, S. A. In
Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Paquestte, L. A., Eds.;
Pergamon: Oxford, 1991; Vol. 4, p 585; (d) Sammelson, R. E.; Kurth, M. J. Chem.
Rev. 2001, 101, 137–202; (e) Hassan, J.; Sevignon, M.; Gozzi, C.; Schulz, E.;
Lemaire, M. Chem. Rev. 2002, 102, 1359–1469; (f) Littke, A. F.; Fu, G. C. Angew.
Chem., Int. Ed. 2002, 41, 4176–4211.
2. (a) Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117–2188; (b) Rieke, R. D.;
Hason, M. V. Tetrahedron 1997, 53, 1925–1956; (c) Organozinc Reagents; Kno-
chel, P., Jones, P., Eds.; Oxford University Press: Oxford, 1999; (d) Erdik, E.
Tetrahedron 1992, 48, 9577–9648.
3. Knochel, P.; Almena Perea, J. J.; Jones, P. Tetrahedron 1998, 54, 8275–8319.
4. (a) Organozinc Reagents: A Practical Appoach; Knochel, P., Jones, P., Eds.; Oxford
University Press: New York, NY, 1999; (b) Knochel, P.; Leuser, H.; Gong, L.-Z.;
Perrone, S.; Kneisel, F. F. In Polyfunctional Zinc Organic Synthesis; Knochel, P.,
Ed.; Handbook of Functionalized Organometallics; Wiley-VCH: Weinheim,
2005; Vol. 1, p 251; (c) Boudier, A.; Bromm, L. O.; Lotz, M.; Knochel, P. Angew.
Chem., Int. Ed. 2000, 39, 4414–4435.
5. (a) Hou, S. Org. Lett. 2003, 5, 423–425; (b) Maezaki, N.; Sawamoto, H.;
Yoshigami, R.; Suzuki, T.; Tanaka, T. Org. Lett. 2003, 5, 1345–1347; (c) Maezaki,
N.; Sawamoto, H.; Suzuki, T.; Yoshigami, R.; Tanaka, T. J. Org. Chem. 2004, 69,
8387–8393.
4.2.17. 5-(3,4-Dimethoxyphenyl)-1,9-dichlorononane 3q
1
Oil; H NMR (400 MHz, CDCl3, 25 ꢁC, TMS):
d
¼7.26 (t, J¼7.8 Hz,
1H), 6.91 (td, J¼14.8, 7.2 Hz, 2H), 3.89 (s, 3H), 3.87 (s, 3H), 3.53–3.47
(m, 4H), 2.50–2.36 (m, 1H),1.80–1.53 (m, 8H),1.36–1.28 (m, 4H); 13C
NMR (100 MHz, CDCl3, 25 ꢁC):
d¼155.6, 138.0, 129.5, 120.3, 111.2,
~
110.5, 55.7, 45.2, 44.9, 36.0, 32.5, 24.8; IR (neat):
n
¼3045, 2935,
2862,1930,1837,1701, 1598,1505,1471,1419,1365,1257,1232,1164,
1145, 1070, 1025, 921, 886, 856, 811, 755, 692, 650, 509 cmꢀ1; MS
(70 eV, EI): m/z (%): 334 (4.6) [Mþþ2], 332 (6.4) [Mþ], 164 (3.5), 151
(100), 107 (6.7), 91 (11.5), 77 (8.9), 55 (9.8). Anal. Calcd (%) for
C17H26Cl2O2 (333.3): C, 61.26; H, 7.86. Found: C, 61.34; H, 7.78.
4.2.18. 5-Phenyl-1,9-dibromononane 3r
Oil; 1H NMR (200 MHz, CDCl3, 25 ꢁC, TMS):
3.37–3.14 (m, 4H), 2.38–2.26 (m, 1H), 2.05–1.80 (m, 6H), 1.7–1.0 (m,
d
¼7.35–7.10 (m, 5H),
6. (a) Sato, T.; Soai, K.; Suzuki, K.; Mukaiyama, T. Chem. Lett. 1978, 601–604; (b)
Mukaiyama, T.; Soai, K.; Sato, T.; Shimizu, H.; Suzuki, K. J. Am. Chem. Soc. 1979,
101, 1455–1460.
7. Nakamura, E.; Aoki, S.; Sekiya, K.; Oshino, H.; Kuwajima, I. J. Am. Chem. Soc. 1987,
109, 8056–8066.
13
6H); C NMR (50 MHz, CDCl3, 25 ꢁC):
d
¼146.4, 128.1, 127.7, 125.7,
~
45.7, 37.1, 31.8, 29.4, 27.6; IR (neat):
n
¼3058, 3025, 2927, 2851, 1651,
1598, 1492, 1440, 1253, 1236, 1216, 1204, 1160, 1072, 743, 693 cmꢀ1
;
8. (a) Soai, K.; Niwa, S. Chem. Rev. 1992, 92, 833–856; (b) Noyori, R.; Kitamura, M.
Angew. Chem., Int. Ed. Engl. 1991, 30, 49–69.
MS (70 eV, EI): m/z (%): 360 (0.2) [Mþ], 227 (1.7), 225 (1.8), 224 (2.7),
147 (1.9), 145 (13), 137 (1.9), 125 (1.9), 91 (100), 77 (13.3), 55 (29.5).
Anal. Calcd (%) for C15H22Br2 (362.1): C, 49.75; H, 6.12. Found: C,
49.87; H, 6.32.
9. Knochel, P.; Yeh, M. C. P.; Berk, S. C.; Talbert, J. J. Org. Chem. 1988, 53, 2390–2392.
10. (a) Micouin, L.; Oestreich, M.; knochel, P. Angew. Chem., Int. Ed. 1997, 36, 245–
246; (b) Jackson, R. F. W.; Turner, D.; Block, M. H. J. Chem. Soc., Perkin Trans. 1
1997, 865–870; (c) Rossi, R.; Bellina, F.; Ciucci, D. J. Organomet. Chem. 1997, 542,
113–120; (d) Jou, D.-C.; Hsiao, T.-Y.; Wu, M.-Y.; Kong, K.-C.; Cheng, C.-H.
Tetrahedron 1998, 54, 1041–1052.
11. (a) Lipshutz, B. H.; Blomgren, P. A. J. Am. Chem. Soc. 1999, 121, 5819–5820; (b)
Lipshutz, B. H.; Blomgren, P. A.; Kim, S.-K. Tetrahedron Lett. 1999, 40, 197–200.
12. Knochel has described a nickel-catalyzed method for effecting sp3–sp3 cou-
plings of primary alkyl iodides and organozinc reagents: (a) Givannini, R.;
Stu¨demann, T.; Devasagayaraj, A.; Dussin, G.; Knochel, P. J. Org. Chem. 1999, 64,
3544–3553; (b) Givannini, R.; Stu¨demann, T.; Dussin, G.; Knochel, P. Angew.
Chem., Int. Ed. 1998, 37, 2387–2390; (c) Devasagayaraj, A.; Stu¨demann, T.;
Knochel, P. Angew. Chem., Int. Ed. Engl. 1995, 34, 2723–2725.
13. (a) Shibata, T.; Tabira, H.; Soai, K. J. Chem. Soc., Perkin Trans. 1 1998, 177–178; (b)
Jones, P.; Knochel, P. J. Org. Chem. 1999, 64, 186–195; (c) Lutz, C.; Jones, P.;
Knochel, P. Synthesis 1999, 312–316; (d) Dosa, P. I.; Fu, G. C. J. Am. Chem. Soc.
1998, 120, 445–446; (e) Kleijn, H.; Rijnberg, E.; Jastrzebski, T. B. H.; Koten, G. V.
Org. Lett. 1999, 1, 853–855.
14. (a) Takeda, T. Modern Carbonyl Olefination; Wiley-VCH: Weinheim, 2004; (b)
Preparation of Alkenes; Williams, J. M. J., Ed.; Oxford University press: 1996.
15. (a) Hu, Y.; Yu, J.; Yang, S.; Wang, J.-X.; Yin, Y. Synlett 1998, 1213–1214; (b) Wang,
J.-X.; Fu, Y.; Hu, Y. Angew. Chem., Int. Ed. 2002, 41, 2757–2760; (c) Wang, J.-X.; Fu,
Y.; Hu, Y. Synthesis 2003, 1506–1510; (d) Wang, J.-X.; Wang, K.; Zhao, L.; Li, H.;
Fu, Y.; Hu, Y. Adv. Synth. Catal. 2006, 348, 1262–1270.
16. For catalyzed-dialkylation reaction, see: (a) Reetz, M. T.; Kyung, S. H. Chem. Ber.
1987, 120, 123; (b) Reetz, M. T.; Westerman, J. J. Org. Chem. 1983, 48, 254–255;
(c) Mayr, H.; Gorath, G. J. Am. Chem. Soc. 1995, 117, 7862–7868; (d) Ishii, A.;
Kotera, O.; Saeki, T.; Mikami, K. Synlett 1997, 1145–1146; (e) Horino, Y.; Naito,
M.; Kimura, M.; Tanaka, S.; Tamaru, Y. Tetrahedron Lett. 2001, 42, 3113–3116.
17. Fang, X.; Watkin, J. G.; Warner, B. P. Tetrahedron Lett. 2000, 41, 447–449.
18. Hu, Y.; Wang, J.-X.; Li, W. Chem. Lett. 2001, 174–175.
4.2.19. Dietheyl 4-phenylheptanedioate 3s
1
Oil; H NMR (400 MHz, CDCl3, 25 ꢁC, TMS):
d
¼7.27 (t, J¼7.2 Hz,
2H), 7.19 (d, J¼6.8 Hz, 1H), 7.10 (d, J¼6.0 Hz, 2H), 4.13–4.01 (m, 4H),
2.56–2.50 (m, 1H), 2.14–2.09 (m, 4H), 2.03–1.98 (m, 2H), 1.89–1.85
13
(m, 2H), 1.23 (t, J¼6.8 Hz, 6H); C NMR (100 MHz, CDCl3, 25 ꢁC,
TMS):
24.3, 14.1; IR (neat):
d
¼173.4, 143.2, 128.5, 127.6, 126.5, 60.2, 60.1, 44.8, 32.3, 31.5,
~
n
¼3061, 3029, 2981, 2932, 1736, 1601, 1496,
1458, 1371, 1350, 1336, 1275, 1245, 1212, 1157, 1116, 1097, 1068, 1027,
967, 750 cmꢀ1; MS (70 eV, EI): m/z (%): 293 (2) [Mþþ1], 292 (10)
[Mþ], 246 (22), 229 (10), 205 (38), 159 (59), 145 (19), 132 (12), 128
(41), 117 (100), 91 (56), 55 (65). Anal. Calcd (%) for C17H24O4 (292.4):
C, 69.84; H, 8.27. Found: C, 69.73; H, 8.46.
4.2.20. 1-Pentyl-1-(2-methoxyphenyl)hexane 3t
Oil; 1H NMR (200 MHz, CDCl3, 25 ꢁC, TMS):
d
¼7.06–6.95 (m, 4H),
3.82 (s, 3H), 2.43–2.40 (m, 1H), 1.66–1.50 (m, 4H), 1.23 (br s, 8H),
1.20–1.03 (m, 4H), 0.85 (t, J¼6.8 Hz, 6H); 13C NMR (50 MHz, CDCl3,
25 ꢁC):
d
¼157.8, 139.5, 127.4, 127.0, 121.0, 113.5, 55.1, 45.2, 37.2, 31.8,
~
27.6, 22.7,14.1; IR (neat):
n
¼2925, 2857,1615,1580,1513,1463,1378,
1305, 1250, 1180, 1109, 1042, 830 cmꢀ1; MS (70 eV, EI): m/z (%): 263