Direct construction of quaternary carbon center utilizing an allylsamarium bromide reagent

Article abstract of DOI:10.1016/S0040-4020(02)00491-X

Direct geminal diallylation of lactones, lactams and acyclic amides containing a N-H bond has been achieved in the presence of allylsamarium bromide. By applying this method, quaternary carbons have been constructed, and 2,2-diallylated cyclic ethers, 2,2-diallylated nitrogen heterocycles and diallylated amides were synthesized in moderate to good yields under mild conditions.

Full text of DOI:10.1016/S0040-4020(02)00491-X

TETRAHEDRON
Pergamon
Tetrahedron 58 =2002) 5301±5306
Direct construction of quaternary carbon center utilizing an
allylsamarium bromide reagent
Zhifang Lia and Yongmin Zhanga,b,p
aDepartment of Chemistry, Zhejiang University, Xixi Campus, Hangzhou 310028, People's Republic of China
bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Science,
Shanghai 200032, People's Republic of China
Received 31 December 2001; revised 18 April 2002; accepted 9May 2002
AbstractÐDirect geminal diallylation of lactones, lactams and acyclic amides containing a N±H bond has been achieved in the presence of
allylsamarium bromide. By applying this method, quaternary carbons have been constructed, and 2,2-diallylated cyclic ethers, 2,2-diallylated
nitrogen heterocycles and diallylated amides were synthesized in moderate to good yields under mild conditions. q 2002 Elsevier Science
Ltd. All rights reserved.
1. Introduction
2. Results and discussion
The addition reaction of organometallics to carbonyl
2.1. The reaction of lactones and phthalic anhydride with
allylic bromide
compounds provides
a fundamental methodology in
synthetic organic chemistry.1 Many metals have been used
in this type of reaction, such as Mg,2 Zn,3 Sn,4 Bi5 and Cd.1
Signi®cant advance in this type reaction has been achieved.
However, when using these metals long reaction times are
required and only reactive halides are effective. Indium in
aqueous medium has shown remarkable facilities in the
allylation of carbonyl groups.6 Samarium diiodide, as a
powerful, versatile, and ether-soluble one-electron donor,
has been widely applied in Barbier±Grignard type reac-
tions,7 and the application of samarium metal has also
stimulated great interest in recent years.8 Aldehydes,
ketones, acid halides and carboxylic acid anhydrides are
widely used as simple starting materials for such transfor-
mations. Usually, homoallylic alcohols were obtained utiliz-
ing these methods, but little attention has been paid to the
geminal diallylation of carbonyl compounds.9 We have
shown that nitriles undergo diallylation on treatment with
allylsamarium bromide to give the corresponding diallyl-
amides.10 However, to the best of our knowledge, transfor-
mations of lactones, lactams and acyclic amides containing
a N±H bond under the action of allylsamarium bromide has
not been investigated.
The reaction of Grignard reagents with lactones was ®rst
investigated by Houben.11 He found that simple aliphatic
g-lactones might be expected to yield glycols, but cyclic
etheri®cation of the primary reaction products of lactones
of this type is apparently relatively rare. Harrowven
reported the addition of allylmagnesium chloride to tetra-
hydrofuranones to give diallylated products under a cooled
=2908C) solution.12 We found that when lactones =1) were
treated with allylsamarium bromide =2) in THF at room
temperature, 2,2-diallylated cyclic ethers =3) were obtained
in good yields =Scheme 1). The lactones and allylsamarium
bromide were used in a ratio of 1:2.2.
All reactions were complete within 5 min with high yields
of diallylated cyclic ethers being isolated. The product
formation was ascertained by TLC monitoring and the
product isolation was achieved by quenching the reaction
with dilute hydrochloric acid followed by extraction. The
We report herein the geminal diallylation of lactones,
lactams and acyclic amides with allylsamarium bromide
to construct quaternary carbons directly.
Keywords: allylsamarium bromide; lactones; lactams; 2,2-diallylated cyclic
ethers.
p
Corresponding author. Tel.: 186-571-5178611; fax: 186-571-8807077;
e-mail: yminzhang@mail.hz.zj.cn
Scheme 1.
0040±4020/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020=02)00491-X

5302
Z. Li, Y. Zhang / Tetrahedron 58 32002) 5301±5306
Table 1. The reaction of lactones and phthalic anhydride with allylic
bromide
Entry
Product
Time =min)
4
Yieldsa =%)
a
9
5
Scheme 2.
Table 2. The reaction of lactams with allylsamarium bromide
0
Entry
b
c
5
4
9
9
Product
Time =min)
Yieldsa =%)
a
5
9
5
0
5
b
c
5
4
5
9
d
e
5
4
85
85
9
5
d
85
f
3
9
5
e
4
5
85
75
a
Isolated yields based on lactones or phthalic anhydride.
reactions were generally clean and no trace of homo-
allylated product could be detected in the H NMR spectra
1
f
of the crude products. However, puri®cation wherever
necessary was performed by ¯ash chromatography. On the
basis of the good results obtained with simple lactones, it
seemed logical to investigate the possibility of extending
this methodology to phthalic anhydride afforded the diallyl-
ated product in good yield =entry f). The results and the
scope of this reaction are summarized in Table 1, which
clearly indicates that the present strategy may afford a
general diallylation protocol for the synthesis of 2,2-diallyl-
ated cyclic ethers from simple lactones.
a
Isolated yields based on lactams.
none, 2-piperidone, piperazinone and caprolactam were
used in this reaction, the corresponding diallylated nitrogen
heterocycles were obtained in excellent yields =Table 2).
But when o-phthalimide =6) and succinimide =7) were
treated with allylsamarium bromide under the same con-
ditions, the diallylated compounds were not detected at
all, with 3-[=Z)-2-propenylidene]-1-isoindolinone =8) and
5-[=Z)-2-propenylidene]-2-pyrrolidinone =9) being obtained,
respectively =Scheme 3).
2.2. The reaction of lactams with allylsamarium bromide
Ï
Lukes reported that the reaction of RMgX with 5±8-
membered lactams led to a mixture of 1-alkyl-1-aza-2-
cyclenes and 2,2-dialkylated =arylated) heterocycles,13 and
the reaction of 2-piperidone with allylmagnesium bromide
led to a compound with unknown structure =C14H23N).14
Recently, Bubnov described the synthesis of 2,2-diallylated
nitrogen heterocycles by the reaction of allylic boranes with
lactams under harsh conditions.15 We found that when
lactams =4) were treated with allylsamarium bromide =2)
in THF at room temperature, 2,2-diallylated nitrogen
heterocycles =5) were obtained in good yields16 =Scheme
2). All reactions were complete within 5 min. The lactams
and allylsamarium bromide were used in a ratio of 1:2.2.
It should be noted that, when lactams, such as, 2-pyrrolidi-
Scheme 3.

Z. Li, Y. Zhang / Tetrahedron 58 32002) 5301±5306
5303
In summary, quaternary carbons are constructed ef®ciently
from lactones, lactams and acyclic amides containing a
N±H bond utilizing allylsamarium bromide. By applying
this method, 2,2-diallylated cyclic ethers, 2,2-diallylated
nitrogen heterocycles and analogous diallylated amides
are obtained under mild conditions, which contain two
double bonds and can be used for the preparation of various
derivatives such as bicyclic compounds and spiro-
compounds.
Scheme 4.
Table 3. The reaction of acyclic amides with allylsamarium bromide
Entry R1
R2
R3
Time =h) Yielda =%)
3. Experimental
a
b
c
d
e
f
g
h
i
CH3
C6H5
C6H5
p-ClC6H4
o-CH3C6H4
CH2C6H5
p-CH3C6H4
H
H
H
H
H
H
H
2
3
4
3
3
4
4
10
3
75
75
75
70
65
50
50
0b
Tetrahydrofuran was distilled from sodium-benzophenone
immediately prior to use. All reactions were conducted
CH3CH2
CH3CH2
CH3CH2
C6H5
under
a
nitrogen atmosphere. Melting points are
1
uncorrected. H NMR spectra were recorded on a Bruker
AC-400 instrument as CDCl3 solutions using TMS as an
internal standard. Chemical shifts =d) are reported in ppm
and coupling constants J are given in Hz. IR spectra were
taken as thin ®lms with a Bruker Vector-22 infrared spectro-
meter. Elemental analyses were performed on an EA-1110
instrument. Metallic samarium and all solvents were
purchased from commercial sources and were used without
further puri®cation. The starting material N-benzanilide was
prepared by published method.17
C6H5
p-CH3C6H4 C6H5
C6H5
C6H5
CH3CH2
H
CH3CH2
H
60c
a
b
c
Isolated yields based on acyclic amides.
The expected compound 9h could not be detected.
Diallyl carbinol was isolated in moderate yield.
It is interesting that acyclic amides =10) containing a N±H
bond also can react with allylsamarium bromide to give the
analogous diallylated amines =11) in moderate to good
yields =Scheme 4). The reaction conditions and scope of
this reaction are shown in Table 3.
3.1. General procedure for the synthesis of 2,2-
diallylated cyclic ethers 03)
Allyl bromide =2.2 mmol) and samarium =2 mmol) with a
catalytic amount of iodine =0.01 mmol) in dry THF =10 mL)
under a nitrogen atmosphere at room temperature. The
mixture was stirred for about 5 min, and a purple color
was formed. Lactones =1 mmol) was added, the purple
color of the mixture disappeared immediately. The reaction
mixture was stirred for 1±5 min and then was quenched
with 0.1 M hydrochloric acid. The resulting mixture was
extracted with diethyl ether =3£10 mL), the diethyl ether
solution was washed with saturated NaCl =2£10 mL) and
dried over anhydrous MgSO4. The solvent was removed by
evaporation under reduced pressure. Puri®cation by column
chromatography on silica gel afforded 2,2-diallylated cyclic
ethers.
As shown in Table 3, acyclic amides =10) containing a N±H
bond undergo the diallylation reaction smoothly, and the
diallylated amides =11) were obtained in moderate to good
yields. But when N,N-diethylbenzamide was treated with
allylsamarium bromide for 10 h under the same conditions,
the expected compound =11h) could not be detected.
A possible mechanism of the diallylation of lactams and
acyclic amides containing a N±H bond is shown in Scheme
5. Firstly, lactams =A) undergo allylation leading to inter-
mediates =B), which eliminate the HOSmBr fragment to
produce imines =C). Then, Sm =III) will work as a Lewis
acid to form iminium ions =D), which would, in turn,
undergo allylation with allylsamarium bromide leading to
the intermediates =E), which was decomposed by water to
produce the desired diallylation products =F).
3.1.1. 2,2-Diallyltetrahydrofuran 03a). Colorless oil;
yield: 144 mg =95%); IR: nmax =liquid ®lm) 1639, 998; H
NMR =400 MHz, CDCl3) d 5.79±5.89 =2H, m, 2£CH),
1
Scheme 5.

5304
Z. Li, Y. Zhang / Tetrahedron 58 32002) 5301±5306
5.08±5.13 =4H, m, 2£CH2v), 3.60 =2H, t, Jˆ5.9Hz,
CH2O), 2.21±2.25 =4H, d, Jˆ7.3 Hz, 2£CH2CHvCH2),
1.51±1.66 =4H, m, 2£CH2); MS: m/z =%) 153 =M111),
135 =15.97), 119 =1.56), 111 =100). Anal. calcd. C10H16O:
C, 78.95; H, 10.53. Found: C, 78.89; H, 10.47%.
was extracted with diethyl ether =3£10 mL), the diethyl
ether solution was washed with saturated NH4Cl
=2£10 mL) and dried over anhydrous MgSO4. The solvent
was removed by evaporation under reduced pressure. The
crude product was puri®ed by preparative TLC on silica gel
=cyclohexane±ethyl acetate =3:1) as eluent).
3.1.2. 2,2-Diallyl-5-methyltetrahydrofuran 03b). Color-
less oil; yield: 149mg =90%); IR: nmax =liquid ®lm) 1639,
998; H NMR =400 MHz, CDCl3) d 5.79±5.88 =2H, m,
3.2.1. 2,2-Diallylpyrrolidine 05a). Colorless liquid;
yield: 144 mg =95%); bp 86±888C =13 Torr);. H NMR
1
1
2£CH), 5.08±5.13 =4H, m, 2£CH2v), 3.74±3.78 =1H, m,
CHCH3), 2.21±2.25 =4H, d, Jˆ7.3 Hz, 2£CH2CHvCH2),
1.25±1.51 =4H, m, 2£CH2), 1.18 =3H, d, Jˆ6.2 Hz, CH3);
MS: m/z =%) 167 =M111), 149=29.11), 125 =100). Anal.
calcd. C11H18O: C, 79.52; H, 10.84. Found: C, 79.48; H,
10.80%.
=400 MHz, CDCl3): d 5.75±5.77 =2H, m, 2£CH), 5.17±
5.20 =4H, m, 2£CH2v), 3.02 =2H, t, Jˆ6.8 Hz, CH2N),
2.38 =4H, d, Jˆ7.3 Hz, 2£CH2CHvCH2), 1.45±1.70
=5H, m, 2£CH21NH); MS: m/z =%): 152 =M11, 2.33),
151 =M1, 4.78), 110 =100). Anal. calcd. C10H17N: C,
79.47; H, 11.26; N, 9.27. Found: C, 79.39; H, 11.29; N,
9.29%.
3.1.3. 2,2-Diallyltetrahydro-2H-pyran 03c). Colorless
oil; yield: 158 mg =95%); IR: nmax =liquid ®lm) 1639,
998; H NMR =400 MHz, CDCl3) d 5.79±5.89 =2H, m,
3.2.2. 2,2-Diallylpiperidine 05b). Colorless liquid; yield:
149mg =90%); bp 66±67 8C =1 Torr); H NMR =400 MHz,
1
1
2£CH), 5.08±5.13 =4H, m, 2£CH2v), 3.62 =2H, t,
Jˆ5.9Hz, CH2O), 2.21±2.25 =4H, d, Jˆ7.3 Hz,
2£CH2CHvCH2), 1.51±1.66 =6H, m, 3£CH2), MS: m/z
=%) 167 =M111), 149=15.79), 133 =1.56), 125 =100).
Anal. calcd. C11H18O: C, 79.52; H, 10.84. Found: C,
79.35; H, 10.57%.
CDCl3): d 5.75±5.77 =2H, m, 2£CH), 5.17±5.20 =4H, m,
2£CH2v), 2.75 =2H, t, Jˆ6.8 Hz, CH2N), 2.34 =4H, d,
Jˆ7.3 Hz, 2£CH2CHvCH2), 1.40±1.55 =7H, m,
3£CH21NH); MS: m/z =%): 166 =M11, 2.33), 165 =M1,
4.78), 124 =100). Anal. calcd. C11H19N: C, 80.00; H, 11.52;
N, 8.48. Found: C, 79.89; H, 11.49; N, 8.40%.
3.1.4. 2,2-Diallyloxepane 03d). Colorless oil; yield: 153 mg
=85%); IR: nmax =liquid ®lm) 1639, 998; 1H NMR
=400 MHz, CDCl3) d 5.79±5.89 =2H, m, 2£CH), 5.08±
5.13 =4H, m, 2£CH2v), 3.62 =2H, t, Jˆ5.9Hz, CH2O),
2.21±2.25 =4H, d, Jˆ7.3 Hz, 2£CH2CHvCH2), 1.49±
1.66 =8H, m, 4£CH2); MS: m/z =%) 181 =M111), 163
=15.97), 147 =1.56), 139 =100). Anal. calcd. C12H20O: C,
80.00; H, 11.11. Found: C, 79.79; H, 10.87%.
3.2.3. 2,2-Diallylpiperazine 05c). Colorless liquid; yield:
158 mg =95%); bp 54±578C =0.2 Torr); 1H NMR
=400 MHz, CDCl3): d 5.75±5.77 =2H, m, 2£CH), 5.17±
5.20 =4H, m, 2£CH2v), 2.65 =4H, s, CH2CH2), 2.5 =2H, s,
CH2N), 2.28 =4H, d, Jˆ7.3 Hz, 2£CH2CHvCH2), 1.50 =2H,
s, 2£NH). Anal. calcd. C10H18N2: C, 72.28; H, 10.84; N,
16.87. Found: C, 72.20; H, 10.85; N, 16.79%.
3.2.4. 2,2-Diallylazepane 05d). Colorless liquid; yield:
152 mg =85%); bp 75±778C =1 Torr); H NMR =400 MHz,
1
3.1.5. 1,1-Diallyl-1,3-dihydroisobenzofuran 03e). Yellow
oil; yield: 170 mg =85%); H NMR =400 MHz, CDCl3) d
1
CDCl3): d 5.75±5.77 =2H, m, 2£CH), 5.17±5.20 =4H,
m, 2£CH2v), 2.65 =2H, t, Jˆ6.8 Hz, CH2N), 2.28 =4H,
d, Jˆ7.3 Hz, 2£CH2CHvCH2), 1.45±1.70 =9H, m,
4£CH21NH); MS: m/z =%): 180 =M11, 2.33), 179
=M1, 4.78), 138 =100). Anal. calcd. C12H21N: C, 80.45;
H, 11.73; N, 7.82. Found: C, 80.38; H, 11.68; N,
7.79%.
7.17±7.25 =4H, m, ArH), 5.62±5.69=2H, m, 2 £CH), 5.04±
5.09=4H, m, 2 £CH2v), 4.73 =2H, s, CH2O), 2.56±2.76 =4H,
d, Jˆ7.3 Hz, 2£CH2CHvCH2); MS: m/z =%) 201 =M111),
183 =3.83), 159 =98.90), 131 =100). Anal. calcd. C14H16O: C,
84.00; H, 8.00; found; C, 83.97; H, 8.05%.
3.1.6. 3,3-Diallyl-1,5-dihydro-1-isobenzofuranone 03f).
Yellow oil; yield: 203 mg =95%); 1H NMR =400 MHz,
CDCl3) d 7.36±7.91 =4H, m, ArH), 5.51±5.57 =2H, m,
2£CH), 5.04±5.09=4H, m, 2 £CH2v), 2.63±2.76 =4H, d,
Jˆ7.3 Hz, 2£CH2CHvCH2); MS: m/z =%) 215 =M1 11),
197 =20.09), 173 =100), 133 =95.72), 117 =78.50), 105
=26.36). Anal. calcd. C14H14O2: C, 78.50; H, 6.54. Found:
C, 78.45; H, 6.49%.
3.2.5. 3-[0Z)-2-Propenylidene]-1-isoindolinone 05e).
White solid; yield: 145 mg =85%); mp 98±1018C; IR:
n
max: 3320 =NH), 1707 =CvO), 1650, 1615 =CvC) cm21
;
1H NMR =400 MHz, CDCl3): d 9.52 =1H, br s, NH), 7.89±
7.27 =4H, m, ArH), 6.81±6.85 =1H, m, CH), 6.23 =1H, d,
Jˆ11.5 Hz, CH), 4.88±5.45 =2H, m, CH2v); MS: m/z =%):
172 =M11, 2.03), 171 =M1, 5.47), 130 =100), 102 =34.15).
Anal. calcd. C11H9NO: C, 77.19; H, 5.26; N, 8.19. Found: C,
77.16; H, 5.20; N, 8.18%.
3.2. General procedure for the synthesis of 2,2-
diallylated nitrogen heterocycles 05)
3.2.6. 5-[0Z)-2-Propenylidene]-1-pyrrolidinone 05f).
White solid; yield: 92 mg =75%); mp 98±1018C; IR: nmax
:
Samarium =0.33 g, 2.2 mmol) and allyl bromide =0.30 g,
2.5 mmol) in THF =20 mL) were added to a three-necked
¯ask with stirring at room temperature under nitrogen.
When the color of the mixture turned into purple, stirring
was continued for 1 h until the samarium powder dis-
appeared, then lactams =1 mmol) were added to the solution,
and the mixture was stirred at room temperature for 5 min.
Five milliliters of water was added. The reaction mixture
3320 =NH), 1700 =CvO), 1650, 1615 =CvC) cm21, H
NMR =400 MHz, CDCl3): d 8.48 =1H, br s, NH), 6.25±
6.34 =1H, m, CH), 5.80 =1H, d, Jˆ7.0 Hz, CH), 5.00±5.05
=2H, m, CH2v), 2.75±2.82 =2H, t, Jˆ6.0 Hz, CH2CvO),
2.53±2.57 =2H, t, Jˆ6.0 Hz, CH2). Anal. calcd. C7H9NO: C,
68.29; H, 7.31; N, 11.38. Found: C, 68.25; H, 7.28; N,
11.30%.
1

Z. Li, Y. Zhang / Tetrahedron 58 32002) 5301±5306
5305
3.3. The reaction of acyclic amides with allylsamarium
bromide
q, Jˆ7.3 Hz, CH2CH3), 0.88 =3H, t, Jˆ7.3 Hz, CH2CH3);
MS: m/z =%): 230 =M11, 8.52), 229=M 1, 4.20), 188 =100),
146 =59.44), 91 =17.00). Anal. calcd. C16H23N: C, 83.79; H,
10.11; N, 6.11. Found: C, 83.56; H, 10.01; N, 5.90%.
Samarium =0.33 g, 2.2 mmol) and allyl bromide =0.30 g,
2.5 mmol) in THF =20 mL) were added to a three-necked
¯ask with stirring at room temperature under nitrogen.
When the color of the mixture turned into purple, stirring
was continued for 1 h until the samarium powder dis-
appeared, then acyclic amides =1 mmol) were added to the
solution, and the mixture was stirred at room temperature
for the appropriate times =Table 3). Five milliliters of water
was added. The reaction mixture was extracted with diethyl
ether =3£10 mL), the diethyl ether solution was washed with
saturated NH4Cl =2£10 mL) and dried over anhydrous
MgSO4. The solvent was removed by evaporation under
reduced pressure. The crude product was puri®ed by
preparative TLC on silica gel =cyclohexane±ethyl acetate
=4:1) as eluent).
3.3.5. N-01-Allyl-1-04-phenyl)-3-butenyl)-N-benzylamine
011e). Yellow oil; yield: 180 mg =65%); IR =liquid ®lm):
n
max: 3410 =NH), 2977, 1639 =RCHvCH2), 1601 cm21
;
1H NMR =400 MHz, CDCl3): d 7.20±7.52 =10H, m, ArH),
5.77±5.84 =2H, m, 2£CH), 5.05±5.10 =4H, m, 2£CH2v),
3.50 =2H, s, CH2NH), 3.45 =1H, br, NH), 2.60±2.62 =4H, d,
Jˆ7.4 Hz, 2£CH2CHvCH2); MS: m/z =%): 278 =M11,
11.99), 277 =M1, 2.99), 236 =100), 91 =73.24). Anal.
calcd. C20H23N: C, 86.59; H, 8.36; N, 5.05. Found: C,
86.45; H, 8.15; N, 5.25%.
3.3.6. N-01-Allyl-1-04-phenyl)-3-butenyl)-N-04-methyl-
phenyl)amine 011f). Yellow oil; yield: 139mg =50%); IR
=liquid ®lm): nmax: 3410 =NH), 2977, 1639 =RCHvCH2),
1601 cm21; 1H NMR =400 MHz, CDCl3): d 7.02±7.42 =9H,
m, ArH), 5.77±5.84 =2H, m, 2£CH), 5.05±5.10 =4H, m,
2£CH2v), 3.45 =1H, br, NH), 2.60±2.62 =4H, d,
Jˆ7.4 Hz, 2£CH2CHvCH2), 2.22 =3H, s, CH3); MS: m/z
=%): 278 =M11, 12.27), 277 =M1, 6.32), 236 =100), 91
=73.24). Anal. calcd. C20H23N: C, 86.59; H, 8.36; N, 5.05.
Found: C, 86.40; H, 8.25; N, 5.20%.
3.3.1.
011a). Yellow oil; yield: 151 mg =75%); IR =liquid ®lm):
max: 3410 =NH), 2977, 1639 =RCHvCH2), 1601 cm21
N-01-Allyl-1-methyl-3-butenyl)-N-phenylamine
n
;
1H NMR =400 MHz, CDCl3): d 7.11±7.21 =2H, m, ArH),
6.71±6.73 =3H, m, ArH), 5.81±5.87 =2H, m, 2£CH), 5.05±
5.11 =4H, m, 2£CH2v), 3.49=1H, br, NH), 2.30±2.47 =4H,
d, Jˆ7.3 Hz, 2£CH2CHvCH2), 1.27 =3H, s, CH3); MS: m/z
=%): 202 =M11, 6.72), 201 =M1, 4.03), 160 =100), 118
=61.75), 77 =27.68). Anal. calcd. C14H19N: C, 83.58; H,
9.45; N, 6.96. Found: C, 83.50; H, 9.35; N, 6.85%.
3.3.7. N-01-Allyl-1-04-methylphenyl)-3-butenyl)-N-phenyl-
amine 011g). Yellow oil; yield: 138 mg =50%); IR =liquid
®lm): nmax
;
:
3410 =NH), 2977, 1639 =RCHvCH2),
1H NMR =400 MHz, CDCl3): d 7.16±7.75
1601 cm21
3.3.2. N-01-Allyl-1-ethyl-3-butenyl)-N-phenylamine 011b).
Yellow oil; yield: 161 mg =75%); IR =liquid ®lm): nmax: 3410
=9H, m, ArH), 6.05±6.11 =2H, m, 2£CH), 5.18±5.23 =4H,
m, 2£CH2v), 3.45 =1H, br, NH), 2.75±2.82 =4H, d,
Jˆ7.4 Hz, 2£CH2CHvCH2), 2.40 =3H, s, CH3); MS: m/z
=%): 278 =M11, 2.27), 277 =M1, 6.32), 236 =7.50), 119
=100), 91 =50.22). Anal. calcd. C20H23N: C, 86.59; H,
8.36; N, 5.05. Found: C, 86.35; H, 8.22; N, 5.16%.
=NH), 2977, 1639 =RCHvCH2), 1601 cm21 1H NMR
;
=400 MHz, CDCl3): d 7.11±7.14 =2H, m, ArH), 6.67±6.71
=3H, m, ArH), 5.78±5.85 =2H, m, 2£CH), 5.05±5.11 =4H, m,
2£CH2v), 3.45 =1H, br, NH), 2.37 =4H, d, Jˆ7.3 Hz,
2£CH2CHvCH2), 1.65 =2H, q, Jˆ7.3 Hz, CH2CH3), 0.88
=3H, t, Jˆ7.3 Hz, CH2CH3); MS: m/z =%): 216 =M11,
1.66), 215 =M1, 2.57), 174 =100), 132 =58.14), 77 =27.42).
Anal. calcd. C15H21N: C, 83.67; H, 9.83; N, 6.50. Found: C,
83.56; H, 9.62; N, 6.44%.
3.3.8. 4-04-Phenyl)-1,6-heptadien-4-ol 011i). Yellow oil;
yield: 113 mg =60%); IR =liquid ®lm): nmax: 3330 =OH),
2977, 1639 =RCHvCH2), 1601 cm21
;
1H NMR
=400 MHz, CDCl3): d 7.32±7.64 =5H, m, ArH), 6.57±5.61
=2H, m, 2£CH), 5.06±5.12 =4H, m, 2£CH2v), 2.49±2.71
=4H, d, Jˆ7.4 Hz, 2£CH2CHvCH2), 2.20 =1H, br, OH).
Anal. calcd. C13H16O: C, 82.94; H, 8.57. Found: C, 82.75;
H, 8.41%.
3.3.3. N-01-Allyl-1-ethyl-3-butenyl)-N-04-chlorophenyl)-
amine 011c). Yellow oil; yield: 188 mg =75%); IR =liquid
®lm): nmax
;
:
3410 =NH), 2977, 1639 =RCHvCH2),
1H NMR =400 MHz, CDCl3): d 7.05±7.07
1601 cm21
=2H, d, Jˆ8.9Hz, ArH), 6.61±6.63 =2H, d, Jˆ8.8 Hz,
ArH), 5.75±5.82 =2H, m, 2£CH), 5.05±5.12 =4H, m,
2£CH2v), 3.45 =1H, br, NH), 2.37 =4H, d, Jˆ7.3 Hz,
2£CH2CHvCH2), 1.65 =2H, q, Jˆ7.3 Hz, CH2CH3), 0.88
=3H, t, Jˆ7.3 Hz, CH2CH3); MS: m/z =%): 251 =3.42), 250
=12.13), 249=4.42), 208 =100), 166 =58.14). Anal. calcd.
C15H21ClN: C, 72.13; H, 8.07; N, 5.61. Found: C, 72.06;
H, 7.85; N, 5.52%.
Acknowledgements
We are grateful to the National Natural Science Foundation
of China =Project No. 29872010) and the NSF of Zhejiang
province for ®nancial support.
References
3.3.4. N-01-Allyl-1-ethyl-3-butenyl)-N-02-methylphenyl)-
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