Platinum-catalyzed allylation of aminonaphthalenes with allylic acetates

Article abstract of DOI:10.1016/j.tet.2006.01.023

The activation of C-O bonds in allylic acetates has been accelerated by carrying out the reactions in the presence of platinum complexes associated with ligands. Platinum-catalyzed allylation of aminonaphthalenes with allylic acetates leads to N-allylic aminonaphthalenes in good yields.

Full text of DOI:10.1016/j.tet.2006.01.023

Tetrahedron 62 (2006) 3752–3760
Platinum-catalyzed allylation of aminonaphthalenes
with allylic acetates
*
Shyh-Chyun Yang, Wei-Hao Feng and Kim-Hong Gan
Graduate Institute of Pharmaceutical Sciences, Kaohsiung Medical University, Kaohsiung 807, Taiwan, ROC
Received 11 November 2005; revised 5 January 2006; accepted 6 January 2006
Abstract—The activation of C–O bonds in allylic acetates has been accelerated by carrying out the reactions in the presence of platinum
complexes associated with ligands. Platinum-catalyzed allylation of aminonaphthalenes with allylic acetates leads to N-allylic
aminonaphthalenes in good yields.
q 2006 Elsevier Ltd. All rights reserved.
1. Introduction
nucleophilic than the more commonly used benzylamine
or stabilized anionic nitrogen nucleophiles.10 We have
recently reported our attempts and some successful
applications of a process involving the C–O bond cleavage
with direct use of allylic alcohols catalyzed by palladium
complexes.11 The reactions should be promoted in the
presence of titanium reagent. However, platinum-catalyzed
allylation has attracted little attraction.12 In this paper, we
wish to report a novel catalysis of platinum complex, which
mediates N-allylation of aminonaphthalenes with allylic
acetates.
A principal goal of organometallic chemistry is the catalytic
synthesis of organic compounds by using the chemistry of
organic ligands covalently bound to transition metals. Most
organometallic chemistry has focused on complexes with
covalent metal–carbon or metal–hydrogen bonds. Tran-
sition metals, in particular palladium and rhodium, have
been workhorse elements in many commercialized catalytic
processes that include hydrogenations, hydroformylations,
acetic acid production, and other C–C and C–H bond
forming processes.1 Although carbon–oxygen, carbon–
nitrogen, or carbon–sulfur bonds are found in the majority
of important organic molecules, catalytic organometallic
reaction chemistry that leads to the formation of carbon-
heteroatom bonds is less common than that forming carbon–
carbon and carbon–hydrogen bonds. Transition metal h3-
allyl complexes, as well as transition metal s-alkyl
complexes, play important roles as active species and key
intermediates in many reactions catalyzed by transition
metal complexes.2 The palladium-catalyzed allylation is a
powerful tool for C–C, C–N, and C–O bond formation,
which has been widely applied to organic chemistry.3 The
processes have been shown to proceed by attack of
nucleophiles on intermediate h3-allylpalladium(II)
complexes generated by oxidative addition of allylic
compounds including halides,4 esters,5 carbonates,6 carba-
mates,7 phosphates,8 and related derivatives9 to a Pd(0)
complex. Aromatic amines have not been used commonly in
allylic amination, presumably because they are less
2. Results and discussion
To evaluate the scope and limitations of the N-allylation of
aminonaphthalenes with allylic acetates, we treated a
mixture of 1-aminonaphthalene (1a, 2 mmol) and allyl
acetate (2a, 1.6 mmol) in the presence of Pt(acac)2
(1 mol%) and PPh3 (4 mol%) in benzene under nitrogen,
at 50 8C for 3 h, N-allyl-1-naphthylamine (3a) was formed
in only 9% yield (entry 1 in Table 1). The reaction, under
reflux, increased the yields of products 3a and N,N-diallyl-
1-naphthylamine (4a) to 75 and 6%, respectively (entry 2).
The reaction gave 91% yield under reflux for 6 h (entry 3). It
was confirmed that the yield was only 3% in the absence of
PPh3 (entry 4). The reaction did not occur in the absence of
the platinum species (entry 5). Among the platinum
catalysts including Pt(acac)2 (entry 2), cis-PtCl2(PhCN)2
(entry 6), cis-PtCl2(PPh3)2 (entry 7), PtCl2 (entry 8),
PtI2 (entry 9), O[Si(CH3)2C]CH2]2Pt (entry 10),
Pt(CH2]CH2)(PPh3)2 (entries 11 and 12), and Pt(PPh3)4
(entries 13 and 14) were used. Pt(acac)2, O[Si(CH3)2-
C]CH2]2Pt, and Pt(CH2]CH2)(PPh3)2 were found to be
Keywords: Platinum-catalyzed; Allylation; Aminonaphthalenes.
*
Corresponding author. Tel.: C886 7 3121101; fax: C886 7 3210683;
e-mail: scyang@kmu.edu.tw
0040–4020/$ - see front matter q 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2006.01.023

S.-C. Yang et al. / Tetrahedron 62 (2006) 3752–3760
Table 1. Reaction of 1-aminonaphthalene (1a) with allyl acetate (2a)a
3753
AcO
2a
+
Pt catalyst
N
NH
NH2
1a
3a
4a
Entry
Platinum catalyst
Ligand
Solvent
Yield (%) (3a:4a)b
1
2
3
4
5
6
7
8
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
—
cis-PtCl2(PhCN)2
cis-PtCl2(PPh3)2
PtCl2
PPh3
PPh3
PPh3
—
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
—
PPh3
—
PPh3
Bu3P
Benzenec
Benzene
Benzened
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzenec
Benzene
Toluenec
Toluene
9 (100:0)
81 (93:7)
91 (93:7)
3 (100:0)
0
57 (99:1)
2 (100:0)
8 (100:0)
1 (100:0)
88 (86:14)
66 (99:1)
90 (96:4)
5 (100:0)
68 (87:13)
32 (100:0)
3 (100:0)
82 (97:3)
71 (96:4)
96 (96:4)
99 (92:8)
90 (96:4)
1 (100:0)
95 (96:4)
91 (97:3)
25 (99:1)
73 (98:2)
69 (98:2)
87 (78:22)
99 (92:8)
82 (87:13)
98 (97:3)
5 (100:0)
85 (81:19)
89 (90:10)
39 (93:7)
85 (95:5)
52 (83:17)
76 (89:11)
58 (85:15)
66 (94:6)
38 (93:7)
4 (100:0)
9
PtI2
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
O[Si(CH3)2C]CH2]2Pt
Pt(CH2]CH2)(PPh3)2
Pt(CH2]CH2)(PPh3)2
Pt(PPh3)4
Pt(PPh3)4
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
Pt(acac)2
(2-MeC6H4)3P
(3-MeC6H4)3P
(4-MeC6H4)3P
(4-FC6H4)3P
(4-ClC6H4)3P
(4-MeOC6H4)3P
[2,6-(MeO)2C6H3]3P
(2-Furyl)3P
(2-Pyridyl)Ph2P
Dpppe
Dppbf
Dpphg
(4-ClC6H4)3P
(4-ClC6H4)3P
(4-ClC6H4)3P
(4-ClC6H4)3P
(4-ClC6H4)3P
(4-ClC6H4)3P
(4-ClC6H4)3P
(4-ClC6H4)3P
(4-ClC6H4)3P
(4-ClC6H4)3P
(4-ClC6H4)3P
(4-ClC6H4)3P
(4-ClC6H4)3P
(4-ClC6H4)3P
(4-ClC6H4)3P
c
CH2Cl2
THFc
THF
Dioxanec
Dioxane
MeCNc
MeCN
DMFc
DMF
HMPAc
HMPA
a
˚
Reaction conditions: 1a (2 mmol), 2a (1.6 mmol), Pt catalyst (0.02 mmol), ligand (0.08 mmol), and MS 4 A in a solvent (5 mL) were refluxed for 3 h.
b Isolated yield.
c Stirred at 50 8C.
d Reflux for 6 h.
e 1,3-Bis(diphenylphosphino)propane.
f
1,4-Bis(diphenylphosphino)butane.
g 1,6-Bis(diphenylphosphino)hexane.
superior. The use of O[Si(CH3)2C]CH2]2Pt as catalyst was
cheaper than palladium reagents and could give good
results. However, using Pt(CH2]CH2)(PPh3)2 or Pt(PPh3)4
with extra PPh3 as catalyst increased the yield of products
(entries 12 and 14). The catalytic reactivity of the phosphine
ligands is likely due to improved catalyst stability. In the
presence of various monodentate ligands including PPh3,
Bu3P, (2-MeC6H4)3P, (3-MeC6H4)3P, (4-MeC6H4)3P, (4-
FC6H4)3P, (4-ClC6H4)3P, (4-MeOC6H4)3P, [2,6-(MeO)2C6-
H3]3P, (2-furyl)3P, and (2-pyridyl)Ph2P (entries 2, and
15–24) showed that (4-FC6H4)3P (entry 19), (4-ClC6H4)3P
(entry 20), (4-MeOC6H4)3P (entry 21), (2-furyl)3P (entry
23), and (2-pyridyl)Ph2P (entry 24) were the most effective
ligands. The bidentate ligand dppp (entry 25) decreased the
yield of products. Dppb (entry 26) and dpph (entry 27) gave
moderate yields of products. It was known that several
factors, such as the solvent and nature of the nucleophile,
can alter the product pattern in metal-catalyzed allylation.13
At 50 8C, in the presence of Pt(acac)2 and (4-ClC6H4)3P,
eight solvents were investigated, CH2Cl2, dioxane, and

3754
S.-C. Yang et al. / Tetrahedron 62 (2006) 3752–3760
Table 2. Reaction of aromatic amines (1b–k) with allyl acetate (2a)a
Entry
1
1
Yieldsb
CH3
CH3
CH3
NH2
NH
N
1b
3b 49%
4b 19%
2c
3d
1b
1b
3b 48%
3b 41%
4b 18%
4b 42%
Br
Br
Br
4
NH
N
NH2
1c
3c 56%
4c 7%
4c 14%
5c
1c
3c 72%
CN
CN
CN
6
7
8
NH2
NH
N
1d
1e
3d 71%
4d 5%
NH2
NH
N
4e 18%
3e 70%
NO2
NH2
NO2
NH
1f
3f 18%
NO2
9e
1f
3f 51%
N
4f 2%
N
N
N
NH2
NH
N
10
1g
4g 14%
3g 81%

S.-C. Yang et al. / Tetrahedron 62 (2006) 3752–3760
3755
Table 2 (continued)
Entry
1
Yieldsb
NH
N
11
1h
3h 42%
N
NH
12
1i
3i 30%
N
H
N
13
1j
3j 53%
N
H
N
14
S
1k
S
3k 32%
a
˚
Reaction conditions: 1 (2 mmol), 2a (1.6 mmol), Pt(acac)2 (0.02 mmol), (4-ClC6H4)3P (0.08 mmol), and MS 4 A in benzene (5 mL) were refluxed for 3 h.
b Isolated yield.
c Compound 2a (4.0 mmol) was used.
d Compound 2a (8.0 mmol) was used.
e Reflux for 24 h.
HMPA gave worst results. The reaction, under reflux,
benzene, toluene, and THF gave the best results (entries
28–42).
(1k), also reacted to give the N-allylamine in moderate yield
(entries 13 and 14).
The results for amination of a number of derivatives of
allylic alcohols 2b–e with 1-aminonaphthalene (1a) using
Pt(acac)2 and (4-ClC6H4)3P are summarized in Table 3.
Amination of trans-2-hexen-1-yl acetate (2b) gave mixtures
of monoallylated, diallylated and regioisomeric amino-
naphthalenes 5, 6, and 7 in yields of 34, 23, and 38%,
respectively (entry 1 in Table 1). These products may all be
derived from the same p-allyl intermediate which can be
attacked at either the C-1 or C-3 position. The reaction is
considered to proceed via p-allylplatinum intermediates.
The loss of the stereochemistry of the starting acetate 2b is
due to a rapid s$h3$s interconversion of the p-allyl
intermediate compared to the rate of amination of this
intermediate. Reaction of aromatic allylic acetate 2c, the
corresponding monoallylated and diallylated products were
formed in overall 97% yields (entry 2). Increasing the
amount of 2c, favored the formation of the diallylated
compound 9 and gave the products in quantitatively yields
(entry 3). With the allyl chloride (2d), produces only 3a in
9% yield (entry 4). Allyl carbonate (2e) gave products in
moderate yields (entry 5).
The results collected in Table 2 show that the amination of
allyl acetate (2a) with aminonaphthalenes using Pt(acac)2
and (4-ClC6H4)3P, giving general good yields of the
corresponding allylic aminonaphthalenes (entries 1–7). As
expected, increasing the relative amount of the allyl alcohol
favored the formation of the diallylated compound (entries
1–3). Using aminonaphthalenes having strong electron-
withdrawing groups, such as the nitro group, gave only 18%
lower chemical yields (entry 8). These differences in
reactivity could be related to the nucleophilicity of the
corresponding aminonaphthalene. 1-Amino-4-nitronaphtha-
lene (1f) gave 53% yield under reflux for 24 h (entry 9); the
lower yield observed may arise from the nature of the nitro
group. The more acidic 1-amino-4-nitronaphthalene (1f) is
probably less reactive in attack on the p-allyl complex.
3-Aminoquinoline (1g) reacted to give the N-allylated
products in excellent yields (entry 10). The sterically more
demanding secondary aminonaphthalenes (1h and 1i) gave
lower yields (entries 11 and 12). Secondary aromatic
amines, such as diphenylamine (1j) and phenothiazine

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S.-C. Yang et al. / Tetrahedron 62 (2006) 3752–3760
Table 3. Reaction of 1-aminonaphthalene (1a) with allylic compounds (2b–e)a
Entry
2
Yieldsb
OAc
2b
N
NH
HN
1
5 34%
7 34%
6 23%
AcO
Ph
2c
2
Ph
HN
8 89%
Ph
N
Ph
9 8%
3c
4
2c
8 46%
3a 9%
9 54%
Cl
2d
3a 57%
4a 4%
OCOOCH3
5
2e
a
˚
Reaction conditions: 1a (2 mmol), 2 (1.6 mmol), Pt(acac)2 (0.02 mmol), (4-ClC6H4)3P (0.08 mmol), and MS 4 A in benzene (5 mL) were refluxed for 3 h.
b Isolated yield.
c Compound 2a (4.0 mmol) was used.
A possible mechanism for the formation of N-allylanilines
from 1 and 2 is illustrated in Scheme 1, in which the
substituent on allylic acetate is omitted. Acetate 2 reacts
with Pt(0) species generated in situ to afford a p-allylpla-
tinum intermediate (10). Subsequently, the reaction of 10
with aminonaphthalene 1 followed by reductive elimination
gives N-allylaminonaphthalene.
catalyst. The amination of allylic acetates worked well with
aminonaphthalenes, giving generally good yields of the
corresponding allylic aminonaphthalenes. Aminonaphthal-
enes with steric constraints gave lower chemical yields.
4. Experimental
3. Conclusion
4.1. General considerations
In summary, we have shown that platinum-catalyzed
allylation of aminonaphthalenes using allylic acetates is a
simple and efficient route for C–N bond formation. The
reaction did not occur in the absence of the platinum
All reactions were carried out under a nitrogen atmosphere.
Solvents were dried and distilled by known methods.
Column chromatography was performed on silica gel. All
melting points were uncorrected. IR absorption spectra were
recorded on a Perkin-Elmer System 2000 FT-IR spectro-
photometer. Proton and carbon-13 NMR were measured
with a Unity-400 or Mercury Plus-400 spectrometer.
Carbon multiplicities were obtained from DEPT experi-
ments. Chemical shifts (d) and coupling constants (Hz) were
measured with respect to TMS or chloroform-d1. MS and
high-resolution mass spectra (HRMS) were taken on
a Thermo-Finnigan trace GC or Finnigan MAT-95XL
instrument, with a direct inlet system.
NHAr
Pt0Ln
3
OAc
2
Pt
L
11
NHAr
Pt
4.2. General procedure for the platinum-catalyzed
allylation of aminonaphthalenes. Reaction with
1-aminonaphthalene (1a)
L
OAc
10
A mixture of 1-aminonaphthalene (1a) (283 mg, 2 mmol),
allyl acetate (2a) (160 mg, 1.6 mmol), Pt(acac)2 (7.8 mg,
˚
0.02 mmol), PPh3 (21 mg, 0.08 mmol) and MS 4 A in
ArNH2
AcOH
benzene (5 mL) was refluxed under nitrogen for 3 h. After
cooling, the reaction mixture was filtered through Celite and
the solvent was distilled under reduced pressure. Column
1
Scheme 1.

S.-C. Yang et al. / Tetrahedron 62 (2006) 3752–3760
3757
chromatography (n-hexane/chloroform 2:1) of the residue
afforded 3a and 4a in 75 and 6% yields, respectively.
133.6 (C), 133.8 (C), 136.7 (CH), 144.7 (C). EI-MS: m/z 237
(MC), 222, 210, 196, 180, 168, 154, 141, 115, 89. EI-HRMS
calcd for C17H19N: 237.1517. Found: 237.1520.
Products 3j11d and 3k11d are known.
4.2.5. N-Allyl-1-(4-bromonaphthyl)amine (3c). Claret
1
4.2.1. N-Allyl-1-naphthylamine (3a). Light yellow thick
oil. IR (KBr): n 3442 cmK1. 1H NMR (400 MHz, CDCl3): d
3.75 (ddd, JZ1.6, 1.6, 5.6 Hz, 2H, CH2), 4.25 (br s, 1H,
NH), 5.12 (ddt, JZ1.6, 1.6, 10.0 Hz, 1H, vinyl H), 5.24 (ddt,
JZ1.6, 1.6, 17.2 Hz, 1H, vinyl H), 5.92 (ddt, JZ5.6, 10.0,
17.2 Hz, 1H, vinyl H), 6.50 (d, JZ7.6 Hz, 1H, ArH), 7.18
(d, JZ8.0 Hz, 1H, ArH), 7.26 (d, JZ7.6 Hz, 1H, ArH), 7.30
(ddd, JZ1.6, 6.8, 8.4 Hz, 1H, ArH), 7.35 (ddd, JZ1.6, 6.8,
8.0 Hz, 1H, ArH), 7.63 (d, JZ8.4 Hz, 1H, ArH), 7.71 (d,
JZ8.0 Hz, 1H, ArH). 13C NMR (100 MHz, CDCl3): d 46.5
(CH2), 104.6 (CH), 116.3 (CH2), 117.4 (CH), 119.8 (CH),
123.3 (C), 124.5 (CH), 125.5 (CH), 126.4 (CH), 128.5 (CH),
134.1 (C), 134.9 (CH), 142.9 (C). EI-MS: m/z 183 (MC),
168, 154, 142, 127, 115, 89, 77. EI-HRMS calcd for
C13H13N: 183.1048. Found: 183.1049.
thick oil. IR (KBr): n 3445 cmK1. H NMR (400 MHz,
CDCl3): d 3.71 (ddd, JZ1.2, 1.6, 5.2 Hz, 2H, CH2), 4.27 (br
s, 1H, NH), 5.14 (ddt, JZ1.2, 1.6, 10.4 Hz, 1H, vinyl H),
5.24 (ddt, JZ1.6, 1.6, 17.2 Hz, 1H, vinyl H), 5.90 (ddt, JZ
5.2, 10.4, 17.2 Hz, 1H, vinyl H), 6.28 (d, JZ8.0 Hz, 1H,
ArH), 7.32 (ddd, JZ1.2, 6.8, 8.4 Hz, 1H, ArH), 7.45 (ddd,
JZ1.2, 6.8, 8.4 Hz, 1H, ArH), 7.50 (d, JZ8.0 Hz, 1H,
ArH), 7.61 (d, JZ8.4 Hz, 1H, ArH), 8.18 (dd, JZ0.8,
8.0 Hz, 1H, ArH). 13C NMR (100 MHz, CDCl3): d 46.4
(CH2), 105.3 (CH), 109.9 (C), 116.7 (CH2), 120.1 (CH),
124.5 (C), 125.2 (CH), 126.9 (CH), 127.6 (CH), 130.2 (CH),
131.9 (C), 134.4 (CH), 142.8 (C). EI-MS: m/z 263 (MCC2),
261 (MC), 248, 246, 222, 220, 195, 193, 180, 167, 155, 140,
126, 114, 77. EI-HRMS calcd for C13H12BrN: 261.0153.
Found: 261.0155.
4.2.2. N,N-Diallyl-1-naphthylamine (4a). Pale yellow oil.
1H NMR (400 MHz, CDCl3): d 3.79 (d, JZ5.6 Hz, 4H,
CH2!2), 5.13 (ddt, JZ1.6, 1.6, 10.4 Hz, 2H, vinyl H), 5.23
(ddt, JZ1.6, 1.6, 17.2 Hz, 2H, vinyl H), 5.86 (ddt, JZ6.0,
10.4, 17.2 Hz, 2H, vinyl H), 7.08 (d, JZ7.2 Hz, 1H, ArH),
7.36 (dd, JZ7.6, 8.0 Hz, 1H, ArH), 7.42–7.47 (m, 2H,
ArH), 7.53 (d, JZ8.0 Hz, 1H, ArH), 7.81 (dd, JZ2.0,
7.2 Hz, 1H, ArH), 8.29 (d, JZ7.2 Hz, 1H, ArH). 13C NMR
(100 MHz, CDCl3): d 56.1 (CH2), 117.2 (CH2), 117.6 (CH),
123.3 (CH), 123.9 (CH), 125.2 (CH), 125.3 (CH), 125.7
(CH), 128.3 (CH), 130.0 (C), 134.8 (C), 135.0 (CH), 147.6
(C). EI-MS: m/z 223 (MC), 208, 198, 182, 180, 167, 155,
141, 127, 115, 101, 77. EI-HRMS calcd for C16H17N:
223.1361. Found: 223.1362.
4.2.6. N,N-Diallyl-1-(4-bromonaphthyl)amine (4c).
Amber thick oil. H NMR (400 MHz, CDCl3): d 3.76 (d,
1
JZ6.0 Hz, 4H, CH2!2), 5.14 (ddt, JZ0.8, 1.2, 10.4 Hz,
2H, vinyl H), 5.22 (ddt, JZ1.6, 1.6, 17.2 Hz, 2H, vinyl H),
5.84 (ddt, JZ6.0, 10.4, 17.2 Hz, 2H, vinyl H), 6.93 (d, JZ
8.0 Hz, 1H, ArH), 7.55 (ddd, JZ1.6, 6.8, 8.0 Hz, 2H, ArH),
7.65 (d, JZ8.0 Hz, 1H, ArH), 8.20 (d, JZ8.0 Hz, 1H, ArH),
8.32 (d, JZ8.4 Hz, 1H, ArH). 13C NMR (100 MHz,
CDCl3): d 56.3 (CH2), 117.0 (C), 117.6 (CH2), 118.5
(CH), 124.3 (CH), 126.1 (CH), 127.2 (CH), 127.6 (CH),
129.3 (CH), 131.4 (C), 132.9 (C), 134.5 (CH), 147.8 (C). EI-
MS: m/z 303 (MCC2), 301 (MC), 288, 286, 260, 245, 234,
232, 222, 207, 195, 180, 167, 153, 126, 113, 82. EI-HRMS
calcd for C16H16BrN: 301.0466. Found: 301.0466.
4.2.3. N-Allyl-1-(2-methylnaphthyl)amine (3b). Red thick
oil. IR (KBr): n 3370 cmK1. 1H NMR (400 MHz, CDCl3): d
2.38 (s, 3H, CH3), 3.27 (br s, 1H, NH), 3.72 (ddd, JZ1.2,
1.6, 6.0 Hz, 2H, CH2), 5.11 (ddt, JZ1.2, 1.6, 10.0 Hz, 1H,
vinyl H), 5.30 (ddt, JZ1.6, 1.6, 17.2 Hz, 1H, vinyl H), 6.03
(ddt, JZ6.0, 10.0, 17.2 Hz, 1H, vinyl H), 7.23 (d, JZ
8.4 Hz, 1H, ArH), 7.35 (ddd, JZ1.2, 6.8, 8.0 Hz, 1H, ArH),
7.41 (ddd, JZ1.6, 6.8, 8.4 Hz, 2H, ArH), 7.73 (d, JZ
8.0 Hz, 1H, ArH), 8.04 (d, JZ8.4 Hz, 1H, ArH). 13C NMR
(100 MHz, CDCl3): d 18.8 (CH3), 52.7 (CH2), 115.8 (CH2),
122.6 (CH), 122.7 (CH), 124.8 (CH), 125.3 (CH), 125.4 (C),
128.2 (CH), 128.5 (C), 129.2 (CH), 133.5 (C), 136.6 (CH),
142.2 (C). EI-MS: m/z 197 (MC), 182, 180, 168, 156, 141,
129, 115, 102, 89, 77. EI-HRMS calcd for C14H15N:
197.1204. Found: 197.1207.
4.2.7. N-Allyl-1-(4-cyanonaphthyl)amine (3d). Light
yellow crystal. Mp: 129–131 8C (CHCl3/n-hexane). IR
1
(KBr): n 3393 cmK1. H NMR (400 MHz, CDCl3): d 4.00
(ddd, JZ1.6, 1.6, 5.2 Hz, 2H, CH2), 5.21 (br s, 1H, NH),
5.27 (ddt, JZ1.6, 1.6, 10.4 Hz, 1H, vinyl H), 5.36 (ddt, JZ
1.6, 1.6, 17.2 Hz, 1H, vinyl H), 6.02 (ddt, JZ5.2, 10.4,
17.2 Hz, 1H, vinyl H), 6.52 (d, JZ8.0 Hz, 1H, ArH), 7.52
(ddd, JZ1.2, 6.8, 8.4 Hz, 1H, ArH), 7.62 (ddd, JZ1.2, 6.8,
8.4 Hz, 1H, ArH), 7.74 (d, JZ8.4 Hz, 1H, ArH), 7.83 (d,
JZ8.4 Hz, 1H, ArH), 8.15 (dd, JZ0.8, 8.4 Hz, 1H, ArH).
13C NMR (100 MHz, CDCl3): d 46.1 (CH2), 96.9 (C), 103.2
(CH), 117.5 (CH2), 119.6 (C), 120.2 (CH), 122.0 (C), 125.9
(CH), 126.0 (CH), 128.2 (CH), 133.4 (CH), 133.5 (C), 134.6
(CH), 147.1 (C). EI-MS: m/z 208 (MC), 193, 181, 167, 154,
140, 125, 113, 90, 77. EI-HRMS calcd for C14H12N2:
208.1000. Found: 208.1003.
4.2.4. N,N-Diallyl-1-(2-methylnaphthyl)amine (4b). Pale
yellow oil. H NMR (400 MHz, CDCl3): d 2.41 (s, 3H,
1
4.2.8. N,N-Diallyl-1-(4-cyanonaphthyl)amine (4d). Light
yellow thick oil. 1H NMR (400 MHz, CDCl3): d 3.88 (ddd,
JZ1.6, 1.6, 5.6 Hz, 4H, CH2!2), 5.21 (ddt, JZ1.2, 1.6,
10.4 Hz, 2H, vinyl H), 5.28 (ddt, JZ1.6, 1.6, 17.2 Hz, 2H,
vinyl H), 5.84 (ddt, JZ5.6, 10.4, 17.2 Hz, 2H, vinyl H), 7.01
(d, JZ8.0 Hz, 1H, ArH), 7.56 (ddd, JZ1.2, 6.8, 8.4 Hz, 1H,
ArH), 7.63 (ddd, JZ1.2, 6.8, 8.0 Hz, 1H, ArH), 7.78 (d, JZ
8.0 Hz, 1H, ArH), 8.19 (ddd, JZ0.4, 0.8, 8.4 Hz, 1H, ArH),
8.26 (ddd, JZ0.4, 0.8, 8.4 Hz, 1H, ArH). 13C NMR
(100 MHz, CDCl3): d 55.7 (CH2), 103.3 (C), 115.5 (CH),
CH3), 3.79 (m, 4H, CH2!2), 4.98 (ddt, JZ1.2, 1.6,
10.0 Hz, 2H, vinyl H), 5.08 (ddt, JZ1.6, 1.6, 17.2 Hz, 2H,
vinyl H), 5.87 (ddt, JZ6.8, 10.0, 17.2 Hz, 2H, vinyl H), 7.19
(d, JZ8.4 Hz, 1H, ArH), 7.32 (ddd, JZ1.2, 6.8, 8.0 Hz, 1H,
ArH), 7.41 (ddd, JZ1.6, 6.8, 8.4 Hz, 1H, ArH), 7.48 (d, JZ
8.4 Hz, 1H, ArH), 7.71 (d, JZ8.0 Hz, 1H, ArH), 8.17 (d,
JZ8.8 Hz, 1H, ArH). 13C NMR (100 MHz, CDCl3): d 19.7
(CH3), 56.5 (CH2), 116.2 (CH2), 124.6 (CH), 124.7 (CH),
125.3 (CH), 125.5 (CH), 128.1 (CH), 129.7 (CH), 133.3 (C),

3758
S.-C. Yang et al. / Tetrahedron 62 (2006) 3752–3760
118.0 (CH2), 118.6 (C), 124.7 (CH), 125.7 (CH), 126.4
(CH), 128.2 (CH), 128.6 (C), 132.7 (CH), 133.7 (CH), 134.0
(C), 152.7 (C). EI-MS: m/z 248 (MC), 233, 221, 205, 192,
179, 166, 152, 140, 125, 99, 82. EI-HRMS calcd for
C17H16N2: 248.1313. Found: 248.1312.
(100 MHz, CDCl3): d 55.8 (CH2), 114.0 (CH), 118.2 (CH2),
123.9 (CH), 124.8 (CH), 125.6 (CH), 126.1 (CH), 127.4 (C),
128.8 (C), 129.3 (CH), 133.5 (CH), 141.8 (C), 154.6 (C). EI-
MS: m/z 268 (MC), 253, 238, 224, 222, 210, 207, 194, 180,
167, 153, 140, 127, 115, 82, 77. EI-HRMS calcd for
C16N16N2O2: 268.1212. Found: 268.1215.
4.2.9. N-Allyl-2-naphthylamine (3e). Brown thick oil. IR
1
(KBr): n 3417 cmK1. H NMR (400 MHz, CDCl3): d 3.64
4.2.13. N-Allyl-3-quinolylamine (3g). Pale yellow thick
1
(br s, 1H, NH), 3.67 (ddd, JZ1.6, 1.6, 5.6 Hz, 2H, CH2),
5.10 (ddt, JZ1.6, 1.6, 10.4 Hz, 1H, vinyl H), 5.21 (ddt, JZ
1.6, 1.6, 17.2 Hz, 1H, vinyl H), 5.85 (ddt, JZ5.6, 10.4,
17.2 Hz, 1H, vinyl H), 6.69 (d, JZ2.8 Hz, 1H, ArH), 6.71
(d, JZ2.4 Hz, 1H, ArH), 7.14 (ddd, JZ1.2, 6.8, 8.0 Hz, 1H,
ArH), 7.30 (ddd, JZ1.2, 6.8, 8.0 Hz, 1H, ArH), 7.54 (m,
2H, ArH), 7.60 (d, JZ8.0 Hz, 1H, ArH). 13C NMR
(100 MHz, CDCl3): d 46.3 (CH2), 104.6 (CH), 116.1
(CH2), 117.8 (CH), 121.8 (CH), 125.8 (CH), 126.1 (CH),
127.4 (C), 127.5 (CH), 128.7 (CH), 134.9 (CH), 135.0 (C),
145.5 (C). EI-MS: m/z 183 (MC), 168, 156, 141, 129, 115,
89, 77. EI-HRMS calcd for C13H13N: 183.1048. Found:
183.1046.
oil. IR (KBr): 3410 cmK1. H NMR (400 MHz, CDCl3): d
3.72 (ddd, JZ1.6, 1.6, 5.2 Hz, 2H, CH2), 4.64 (br s, 1H,
NH), 5.13 (ddt, JZ1.6, 1.6, 10.4 Hz, 1H, vinyl H), 5.24 (ddt,
JZ1.6, 1.6, 17.2 Hz, 1H, vinyl H), 5.86 (ddt, JZ5.6, 10.0,
17.2 Hz, 1H, vinyl H), 6.90 (d, JZ2.8 Hz, 1H, ArH), 7.32–
7.38 (m, 2H, ArH), 7.52–7.56 (m, 1H, ArH), 7.92–7.97 (m,
1H, ArH), 8.43 (d, JZ2.8 Hz, 1H, ArH). 13C NMR
(100 MHz, CDCl3): d 45.6 (CH2), 110.0 (CH), 116.3
(CH2), 124.5 (CH), 125.7 (CH), 126.6 (CH), 128.3 (CH),
129.3 (C), 133.9 (CH), 141.3 (CH), 141.3 (C), 141.4 (C),
142.9 (CH). EI-MS: m/z 185 (MC), 169, 157, 143, 128, 116,
101, 89, 75, 63. EI-HRMS calcd for C12H12N2: 184.1000.
Found: 184.0996.
4.2.10. N,N-Diallyl-2-naphthylamine (4e). Light yellow
thick oil. 1H NMR (400 MHz, CDCl3): d 4.02 (ddd, JZ1.6,
2.0, 4.8 Hz, 4H, CH2!2), 5.18 (ddt, JZ1.6, 2.0, 10.0 Hz,
2H, vinyl H), 5.24 (ddt, JZ1.6, 1.6, 17.2 Hz, 2H, vinyl H),
5.91 (ddt, JZ4.8, 10.0, 17.2 Hz, 2H, vinyl H),6.92 (s, 1H,
ArH), 7.08 (d, JZ8.0 Hz, 1H, ArH), 7.18 (ddd, JZ2.0, 6.8,
8.0 Hz, 1H, ArH), 7.31–7.36 (m, 1H, ArH), 7.61 (d, JZ
8.4 Hz, 1H, ArH), 7.65 (s, 1H, ArH), 7.67 (d, JZ2.4 Hz, 1H,
ArH). 13C NMR (100 MHz, CDCl3): d 52.9 (CH2), 106.0
(CH), 116.1 (CH2), 116.2 (CH), 121.8 (CH), 126.1 (CH),
126.2 (CH), 126.2 (C), 127.4 (CH), 128.7 (CH), 133.9 (CH),
135.5 (C), 146.5 (C). EI-MS: m/z 223 (MC), 208, 196, 180,
167, 155, 141, 127, 115, 101, 89, 77. EI-HRMS calcd for
C16H17N: 223.1361. Found: 223.1361.
4.2.14. N,N-Diallyl-3-quinolinylamine (4g). Yellow thick
oil. H NMR (400 MHz, CDCl3): d 4.05 (ddd, JZ1.6, 1.6,
1
4.8 Hz, 4H, CH2!2), 5.22 (ddt, JZ1.6, 1.6, 10.0 Hz, 2H,
vinyl H), 5.24 (ddt, JZ1.6, 1.6, 17.6 Hz, 2H, vinyl H), 5.90
(ddt, JZ4.8, 10.0, 17.6 Hz, 2H, vinyl H), 7.14 (d, JZ
2.8 Hz, 1H, ArH), 7.37–7.43 (m, 2H, ArH), 7.58–7.62 (m,
1H, ArH), 7.91–7.95 (m, 1H, ArH), 8.62 (d, JZ2.8 Hz, 1H,
ArH). 13C NMR (100 MHz, CDCl3): d 52.9 (CH2), 112.6
(CH), 116.8 (CH2), 125.0 (CH), 126.0 (CH), 126.8 (CH),
128.7 (CH), 129.2 (C), 133.0 (CH), 141.1 (CH), 141.3 (C),
142.1 (C). EI-MS: m/z 224 (MC), 209, 197, 183, 168, 156,
142, 128, 115, 101, 89, 75, 63. EI-HRMS calcd for
C15H16N2: 224.1313. Found: 224.1314.
4.2.15. N-Allyl-N-ethyl-1-naphthylamine (3h). Light
green thick oil. H NMR (400 MHz, CDCl3): d 1.01 (t,
1
4.2.11. N-Allyl-1-(4-nitronaphthyl)amine (3f). Orange-
red crystal. Mp: 142–143.5 8C (EtOAc/n-hexane). IR (KBr):
n 3391 cmK1. 1H NMR (400 MHz, CDCl3): d 4.06 (ddd, JZ
1.6, 1.6, 5.2 Hz, 2H, CH2), 5.20 (br s, 1H, NH), 5.30 (ddt,
JZ1.2, 1.6, 10.4 Hz, 1H, vinyl H), 5.37 (ddt, JZ1.2, 1.6,
17.2 Hz, 1H, vinyl H), 6.02 (ddt, JZ5.2, 10.4, 17.2 Hz, 1H,
vinyl H), 6.49 (d, JZ8.8 Hz, 1H, ArH), 7.53 (ddd, JZ1.2,
6.8, 8.4 Hz, 1H, ArH), 7.69 (ddd, JZ1.2, 6.8, 8.8 Hz, 1H,
ArH), 7.84 (dd, JZ0.8, 8.4 Hz, 1H, ArH), 8.43 (d, JZ
8.8 Hz, 1H, ArH), 9.02 (dd, JZ0.8, 8.8 Hz, 1H, ArH). 13C
NMR (100 MHz, CDCl3): d 46.2 (CH2), 101.8 (CH), 117.9
(CH2), 120.0 (CH), 121.8 (C), 124.9 (CH), 125.8 (CH),
127.6 (C), 129.3 (CH), 129.6 (CH), 132.9 (CH), 135.1 (C),
149.3 (C). EI-MS: m/z 228 (MC), 193, 180, 167, 154, 140,
129, 114, 102, 88, 77. EI-HRMS calcd for C13N12N2O2:
228.0899. Found: 228.0898.
JZ7.2 Hz, 3H, CH3), 3.18 (q, JZ7.2 Hz, 2H, CH2), 3.70
(ddd, JZ1.2, 1.6, 6.0 Hz, 2H, CH2), 5.09 (ddt, JZ1.2, 2.0,
10.4 Hz, 1H, vinyl H), 5.22 (ddt, JZ1.6, 2.0, 17.2 Hz, 1H,
vinyl H), 5.88 (ddt, JZ6.0, 10.4, 17.2 Hz, 1H, vinyl H), 7.06
(dd, JZ1.2, 7.6 Hz, 1H, ArH), 7.34 (dd, JZ7.6, 8.0 Hz, 1H,
ArH), 7.38–7.46 (m, 2H, ArH), 7.50 (d, JZ8.4 Hz, 1H,
ArH), 7.76 (dd, JZ2.0, 7.6 Hz, 1H, ArH), 8.30 (dd, JZ1.2,
8.0 Hz, 1H, ArH). 13C NMR (100 MHz, CDCl3): d 12.0
(CH3), 46.7 (CH2), 57.3 (CH2), 116.7 (CH2), 117.6 (CH),
123.3 (CH), 124.0 (CH), 125.1 (CH), 125.4 (CH), 125.6
(CH), 128.2 (CH), 130.6 (C), 134.9 (C), 135.6 (CH), 147.7
(C). EI-MS: m/z 211 (MC), 196, 184, 168, 155, 141, 127,
115, 89, 77, 63. EI-HRMS calcd for C15H17N: 211.1361.
Found: 211.1360.
4.2.16. N-Allyl-N-phenyl-1-naphthylamine (3i). Pale
yellow thick oil. 1H NMR (400 MHz, CDCl3): d 4.38
(ddd, JZ1.6, 1.6, 5.2 Hz, 2H, CH2), 5.18 (ddt, JZ1.6, 1.6,
10.4 Hz, 1H, vinyl H), 5.30 (ddt, JZ1.6, 1.6, 17.2 Hz, 1H,
vinyl H), 6.04 (ddt, JZ5.2, 10.4, 17.2 Hz, 1H, vinyl H), 6.58
(dd, JZ0.8, 8.0 Hz, 2H, ArH), 6.70 (ddd, JZ0.8, 6.8,
7.6 Hz, 1H, ArH), 7.12 (ddd, JZ2.0, 7.2, 8.4 Hz, 2H, ArH),
7.39–7.51 (m, 4H, ArH), 7.79 (d, JZ8.0 Hz, 1H, ArH), 7.86
(d, JZ8.4 Hz, 1H, ArH), 7.90 (d, JZ8.0 Hz, 1H, ArH). 13C
NMR (100 MHz, CDCl3): d 55.2 (CH2), 113.7 (CH), 116.8
4.2.12. N,N-Diallyl-1-(4-nitronaphthyl)amine (4f).
Orange-red thick oil. H NMR (400 MHz, CDCl3): d 3.93
1
(ddd, JZ1.2, 1.6, 6.0 Hz, 4H, CH2!2), 5.24 (ddt, JZ1.2,
1.6, 10.0 Hz, 2H, vinyl H), 5.30 (ddt, JZ1.6, 1.6, 17.2 Hz,
2H, vinyl H), 5.86 (ddt, JZ5.6, 10.4, 17.2 Hz, 2H, vinyl H),
6.99 (d, JZ8.8 Hz, 1H, ArH), 7.56 (ddd, JZ1.6, 7.2,
8.4 Hz, 1H, ArH), 7.68 (ddd, JZ1.6, 7.2, 8.4 Hz, 1H, ArH),
8.27 (d, JZ8.4 Hz, 1H, ArH), 8.29 (dd, JZ0.8, 8.0 Hz, 1H,
ArH), 8.75 (dd, JZ0.8, 8.8 Hz, 1H, ArH). 13C NMR

S.-C. Yang et al. / Tetrahedron 62 (2006) 3752–3760
3759
(CH2), 117.1 (CH), 123.8 (CH), 126.2 (CH), 126.3 (CH),
126.4 (CH), 126.5 (CH), 126.9 (CH), 128.5 (CH), 128.9
(CH), 131.4 (C), 134.5 (CH), 135.2 (C), 143.7 (C), 149.2
(C). EI-MS: m/z 259 (MC), 244, 218, 189, 167, 154, 127,
104, 89, 77. EI-HRMS calcd for C19H17N: 259.1361.
Found: 259.1359.
CDCl3): d 46.2 (CH2), 104.8 (CH), 117.6 (CH), 119.9 (CH),
123.4 (C), 126.6 (CH), 125.7 (CH), 126.3 (CH), 126.5 (CH),
126.5 (CH), 127.5 (CH), 128.5 (CH), 128.6 (CH), 131.7
(CH), 134.2 (C), 136.7 (C), 143.0 (C). EI-MS: m/z 259
(MC), 242, 215, 181, 168, 154, 143, 127, 117, 91, 77. EI-
HRMS calcd for C19H17N: 259.1361. Found: 259.1361.
4.2.17. N-(Hex-2E-enyl)-1-naphthylamine (5). Grass-
4.2.21. N,N-Di(3-phenylallyl)-1-naphthylamine (9).
Amber thick oil. H NMR (400 MHz, CDCl3): d 3.95 (d,
green thick oil. IR (KBr): n 3432 cmK1 1H NMR
.
1
(400 MHz, CDCl3): d 0.89 (t, JZ7.2 Hz, 3H, CH3), 1.39
(hext, JZ7.2 Hz, 2H, CH2), 2.01 (dt, JZ6.4, 7.2 Hz, 2H,
CH2), 3.77 (dd, JZ0.8, 6.0 Hz, 2H, CH2), 4.22 (br s, 1H,
NH), 5.63 (dt, JZ5.6, 15.2 Hz, 1H, vinyl H), 5.72 (dt, JZ
6.4, 15.2 Hz, 1H, vinyl H), 6.57 (d, JZ7.2 Hz, 1H, ArH),
7.20 (d, JZ8.4 Hz, 1H, ArH), 7.30 (dd, JZ7.6, 8.0 Hz, 1H,
ArH), 7.34–7.40 (m, 2H, ArH), 7.73 (ddd, JZ1.2, 8.0,
8.0 Hz, 2H, ArH). 13C NMR (100 MHz, CDCl3): d 13.7
(CH3), 22.3 (CH2), 34.4 (CH2), 46.2 (CH2), 104.6 (CH),
117.3 (CH), 119.9 (CH), 123.4 (C), 124.5 (CH), 125.6 (CH),
126.5 (CH), 126.5 (CH), 128.5 (CH), 133.6 (CH), 134.2 (C),
143.2 (C). EI-MS: m/z 225 (MC), 196, 182, 168, 165, 143,
127, 115, 89, 77. EI-HRMS calcd for C16H19N: 225.1517.
Found: 225.1513.
JZ6.0 Hz, 4H, CH2!2), 6.25 (dt, JZ1.6, 16.0 Hz, 2H,
vinyl H), 6.54 (d, JZ16.0 Hz, 2H, vinyl H), 7.09–7.14 (m,
1H, ArH), 7.16 (dd, JZ1.2, 7.2 Hz, 2H, ArH), 7.23 (t, JZ
7.6 Hz, 4H, ArH), 7.29 (dd, JZ1.6, 7.2 Hz, 4H, ArH), 7.34
(dd, JZ7.6, 8.0 Hz, 1H, ArH), 7.43 (ddd, JZ1.2, 1.6,
8.0 Hz, 1H, ArH), 7.48 (dd, JZ1.2, 8.0 Hz, 1H, ArH), 7.51
(d, JZ8.0 Hz, 1H, ArH), 7.79 (d, JZ8.0 Hz, 1H, ArH), 8.38
(d, JZ8.0 Hz, 1H, ArH). 13C NMR (100 MHz, CDCl3): d
55.6 (CH2), 117.7 (CH), 123.4 (CH), 123.9 (CH), 125.3
(CH), 125.4 (CH), 125.7 (CH), 126.3 (C), 126.7 (CH), 127.3
(CH), 128.3 (CH), 128.5 (CH), 129.8 (C), 132.4 (CH), 134.9
(C), 137.0 (C), 147.7 (CH). EI-MS: m/z 375 (MC), 284, 270,
258, 256, 241, 229, 217, 194, 180, 169, 154, 141, 127, 117,
115, 91, 77, 65, 51. EI-HRMS calcd for C28H25N: 375.1987.
Found: 375.1987.
4.2.18. N,N-Di(hex-2E-enyl)-1-naphthylamine (6). Pale
1
yellow oil. H NMR (400 MHz, CDCl3): d 0.84 (t, JZ
7.2 Hz, 6H, CH3!2), 1.34 (hext, JZ7.2 Hz, 4H, CH2!2),
1.96 (dt, JZ6.8, 7.2 Hz, 4H, CH2!2), 3.72 (d, JZ6.4 Hz,
4H, CH2!2), 5.46 (dt, JZ6.4, 15.2 Hz, 2H, vinyl H), 5.58
(dt, JZ6.8, 15.2 Hz, 2H, vinyl H), 7.03 (d, JZ7.2 Hz, 1H,
ArH), 7.35 (dd, JZ7.6, 8.0 Hz, 1H, ArH), 7.40–7.47 (m,
2H, ArH), 7.49 (d, JZ8.4 Hz, 1H, ArH). 13C NMR
(100 MHz, CDCl3): d 13.6 (CH3), 22.5 (CH2), 34.5 (CH2),
55.2 (CH2), 117.7 (CH), 122.9 (CH), 124.1 (CH), 125.0
(CH), 125.3 (CH), 125.5 (CH), 126.6 (CH), 128.2 (CH),
130.1 (C), 133.6 (CH), 134.8 (C), 148.1 (C). EI-MS: m/z 307
(MC), 278, 264, 250, 225, 194, 182, 165, 154, 143, 127,
115, 77. EI-HRMS calcd for C22H29N: 307.2300. Found:
307.2303.
Acknowledgements
We gratefully acknowledge the National Science Council of
the Republic of China for financial support.
References and notes
´
1. (a) Gagne, M. R.; Nolan, S. P.; Marks, T. J. Organometallics
1990, 9, 1716–1718. (b) Walsh, P. J.; Baranger, A. M.;
Bergman, R. G. J. Am. Chem. Soc. 1992, 114, 1708–1719. (c)
McGrane, P. L.; Jensen, M.; Livinghouse, T. J. Am. Chem.
Soc. 1992, 114, 5459–5460. (d) Baranger, A. M.; Walsh, P. J.;
Bergman, R. G. J. Am. Chem. Soc. 1993, 115, 2753–2763. (e)
Brunet, J.; Commenges, G.; Neibecker, D.; Philippot, K.
J. Organomet. Chem. 1994, 469, 221–222.
4.2.19. N-(1-Propylallyl)-1-naphthylamine (7). Dark
brown thick oil. IR (KBr): n 3446 cmK1 1H NMR
.
(400 MHz, CDCl3): d 0.97 (t, JZ7.2 Hz, 3H, CH3), 1.45–
1.56 (m, 2H, CH2), 1.73 (dt, JZ6.8, 14.4 Hz, 2H, CH2),
4.01 (dt, JZ6.4, 6.4 Hz, 1H, CH), 4.38 (br s, 1H, NH), 5.15
(ddd, JZ1.2, 1.2, 10.0 Hz, 1H, vinyl H), 5.25 (d, JZ
17.2 Hz, 1H, vinyl H), 5.83 (ddd, JZ6.0, 10.0, 17.2 Hz, 1H,
vinyl H), 6.63 (d, JZ6.4 Hz, 1H, ArH), 7.20–7.24 (m, 1H,
ArH), 7.31 (dd, JZ7.6, 8.0 Hz, 1H, ArH), 7.41–7.46
(m, 2H, ArH), 7.76–7.84 (m, 2H, ArH). 13C NMR
(100 MHz, CDCl3): d 14.0 (CH3), 19.2 (CH2), 38.0 (CH2),
55.8 (CH), 105.4 (CH), 115.3 (CH2), 117.1 (CH), 119.7
(CH), 123.3 (C), 124.6 (CH), 125.6 (CH), 126.5 (CH), 128.7
(CH), 134.3 (C), 139.7 (CH), 142.3 (C). EI-MS: m/z 225
(MC), 182, 165, 154, 143, 127, 115, 89, 77. EI-HRMS calcd
for C16H19N: 225.1517. Found: 225.1513.
2. Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G.
Principles and Applications of Organotransition Metal
Chemistry; University Science Books: Mill Valley, CA, 1987.
˚
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1
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