Reactivity of AllylSmBr/HMPA: Facile Synthesis of 3-Aryl-1,2,4- benzotriazines

Article abstract of DOI:10.1002/cjoc.201200989

3-Aryl-1,2,4-benzotriazines were conveniently prepared in moderate to good yields from 1,l-bis(benzotriazol-1-yl)methylarenes with allylsamarium bromide/hexamethylphosphramide (allylSmBr/HMPA). Preliminary results indicate that HMPA may enhance the reduci

Full text of DOI:10.1002/cjoc.201200989

FULL PAPER
DOI: 10.1002/cjoc.201200989
Reactivity of AllylSmBr/HMPA: Facile Synthesis of
3-Aryl-1,2,4-benzotriazines†
Ruifeng Yin,a,b Liejin Zhou,a Huili Liu,a,b Hui Mao,a Xin Lü,*,a and Xiaoxia Wang*a,b
a College of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua, Zhejiang 321004, China
b Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese
Academy of Sciences, 345 Lingling Road, Shanghai 200032, China
3-Aryl-1,2,4-benzotriazines were conveniently prepared in moderate to good yields from 1,l-bis(benzotriazol-1-
yl)methylarenes with allylsamarium bromide/hexamethylphosphramide (allylSmBr/HMPA). Preliminary results in-
dicate that HMPA may enhance the reducing ability as well as prohibit the nucleophicility of allylSmBr, thus mak-
ing allylSmBr/HMPA as a promising single-electron transfer (SET) reagent.
Keywords benzotriazines, samarium, allyl bromide, hexamethylphosphramide (HMPA), reduction
Introduction
could also be prepared form oxidation of N-phenyl-
sulfonyl-N''-arylbenzamidrazones with mercury(II) ox-
ide through a diazonium intermediate,[5b] or from the
Pt/C-catalyzed hydrogenation of the 2-nitrophenyl-
hydrazono-ethers.[5c] There are some other methods, but
they are subjected to either not realidy available starting
materials, harsh conditions, extremely low yields, or
few limited examples.[5d-5h]
Herein, we present a modified procedure for the
preparation of 3-aryl-1,2,4-benzotriazines based on our
previous report.[4] Investigations were also carried out to
clarify the enhancement of the reactivity of allylSmBr
by HMPA.
SmI2 is a well-known single-electron transfer (SET)
agent and has been utilized in a broad range of reductive
or coupling reactions.[1] In contrast, the divalent samar-
ium species such as allylsamarium bromide (allylSmBr)
was commonly utilized as a strong nucleophilic organo-
metallic reagent that undergoes a variety of nucleophilic
addition and substitution reactions.[2] AllylSmBr, how-
ever, has not been used as a reductant until recently.[3-4]
Zhang et al reported the transformation of γ-halo-α,β-
unsaturated ketones/esters into 1,4-dienes/trienes using
allylSmBr, which acted as both nucleophilic and SET
reagent.[3] We also unexpectedly isolated 3-aryl-1,2,4-
benzotriazines, resulting from ring-expansion of
1,l-bis(benzotriazo1-1-yl) methylarenes by treatment
with allylSmBr. A probable SET mechanism was pro-
posed therein based on the fact that by treatment of the
substrate with the typical SET reagent SmI2, the desired
3-phenyl-1,2,4-benzotriazine was also obtained in mod-
erate yield (52% with 6.6 equiv. of SmI2 vs. 40% with
2.2 equiv. of allylSmBr).[4]
However, improvement on the preparation of
3-aryl-1,2,4-benzotriazines is still in demand in view of
the unsatisfactory yields (29%－55%) or the require-
ment of large excess SmI2.
Literature survey reveals that several methods have
been available for the preparation of 3-aryl-1,2,4-benzo-
triazines. Huang group[5a] reported very recently that
copper-catalyzed domino reaction of 2-haloanilines with
hydrazides allowed facile access to the triazines gener-
ally in 30%－65% yields. 3-Aryl-1,2,4-benzotriazines
Results and Discussion
In the efforts to improve the yields of 3-aryl-1,2,4-
benzotriazines (2a), gem-dibenzotriazolyl compound 1a
was chosen as the model substrate and a series of reac-
tion conditions were examined. These results were sur-
veyed in Table 1. The use of 2.2 equiv. of SmI2 afforded
3-phenyl-1,2,4-benzotriazine (2a) only in 30% yield
together with 38% yield of the by-product 3a, which
may result from reductive debenzotriazolation followed
by hydrogen abstraction (Entry 1). Suppression on the
formation of 3a by using CH3CN,[6] THP (tetrahydro-
pyran)[7] and benzene[8] was tested. Unfortunately, the
reaction in CH3CN failed to give any desired product
(Entry 5). The use of benzene and THP as solvent led to
lower yields (Entries 3 and 4). Since it was reported that
the existence of excess Sm powder in the in situ gener-
ated solution of SmI2 in THF was a more powerful SET
*
E-mail: wangxiaoxia@zjnu.cn; lvxin@zjnu.cn; Fax: 0086-0579-82282269
Received October 11, 2012; accepted November 21, 2012; published online December 28, 2012.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201200989 or from the author.
Dedicated to the Memory of Professor Weishan Zhou.
†
Chin. J. Chem. 2013, 31, 143—148
© 2013 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
143

Yin et al.
FULL PAPER
reagent,[9] combination of Sm/SmI2 was also examined.
In this case, the yield of 2a was slightly improved (Ta-
ble 1, Entry 6).
gem-dibenzotriazolyl compound into 3-aryl-1,2,4-
bezotriazine. In an oxidation potential study by Flowers
group,[12] the addition of 4 equiv. of HMPA to SmI2 had
a drastic effect on the redox potential increasing the
oxidation potential from −1.33 to −2.05 V, while further
addition of HMPA showed no effect on the redox po-
tential. Therefore allylSmBr/HMPA (1∶4) may also
have the strongest redox potential as has been detected
to be (−2.60±0.01) V.[11]
With the optimized conditions in hand, the reaction
scope was then investigated. As summarized in Table 2,
the substrates 1 with either electron-donating or elec-
tron-withdrawing groups generally afforded the desired
products 2 in moderate to good yields. It was worth
mentioning that the substrate 1k with styrenyl also af-
forded 2k in a reasonable yield (Entry 11), indicating
the tolerance of the C＝C bond to certain extent. How-
ever, compound 1l with an ortho-chloro substituent af-
forded 2a, the ring expanded product accompanied by
dechlorination, in 33% yield while no rearranged prod-
uct was detected and only 3l was isolated in 68% yield
in the absence of HMPA (Entry 12). Interestingly, the
para- or meta-halogen on the aryl remained intact under
the optimized conditions (Entries 7−9). Substrates 1m
and 1n, with strong electron-withdrawing substituents
therein, failed to afford the desired benzotriazines (En-
tries 13, 14), showing the limitation of the method.
However, heteroaryl substrate 1o could give the corre-
sponding benzotriazine 3o in moderate yield (Entry 15).
Table 1 Optimization of the conditions for the preparation of
2a
N
N
N
N
N
N
N
N
Reductant
N
+
Additive
Solvent
H
1a
2a
N
N
N
3a
Yieldc/%
Entrya Reagentb
Additive
Solvent
2a
30
52
3a
1
2
3
4
5
6
SmI2
SmI2
SmI2
SmI2
SmI2
－
－
－
－
－
THF
THF
38
d
31
Benzene 35
16
THP
38
18
CH3CN
THF
n.d.e
n.d.e
f
Sm/SmI2
－
48
40
HMPA (8.8
equiv.)
7
SmI2
THF
THF
THF
THF
49
36
HMPA (6.6
equiv.)
HMPA (8.8
equiv.)
HMPA (11
equiv.)
8
AllylSmBr
AllylSmBr
AllylSmBr
59 (40)g 31 (49)g
67 (40)g 25 (49)g
9
Table 2 Preparation of 3-aryl-1,2,4-benzotriazines from 1 with
allylSmBr/HMPA
10
68
28
N
N
N
N
SmBr
N
N
N
N
a Reaction conditions: substrate 1a (1.0 mmol), Sm(II) reagent
(2.2 equv.), solvent (20 mL), r.t., overnight; b Sm(II) reagent (2.2
+
N
Ar
HMPA, THF
H
Ar
c
2
equiv.) was used unless otherwise specified; Isolated yields
1
based on 1,l-bis(benzotriazol-1-yl)methyl-benzene; d 6.6 equiv. of
Ar
N
e
SmI2 was used; n.d.＝not detected; f The combination of Sm
N
N
(1.1 equiv.) and SmI2 (2.2 equiv.) was used; g The yields in the
parentheses referred to results obtained without HMPA in ref. 4.
3
Entrya Ar of 1
Yield of 2b/%
2a, 67 (40)
Yield of 3b/%
3a, 25 (49)
SmI2/HMPA system was also applied due to the fact
that HMPA[10] could enhance the reactivity of SmI2.
However, only a comparable yield with that of Sm/SmI2
was obtained (Entries 6 and 7). We then turned to allyl-
SmBr/HMPA, a system recently developed by our
group that could efficiently facilitate the reductive cou-
pling between alkenes and esters.[11] Encouragingly,
19% higher yield of 2a was observed (Table 1, Entry 8)
with allylSmBr/HMPA (1∶3, molar ratio). Subsequent
alteration of the ratio of allylSmBr/HMPA to 1∶4 re-
sulted in 67% yield of 2a, which is 27% higher than the
yield obtained without HMPA (Entry 8 vs. 9). Further
increase of HMPA did not produce significant im-
provement (Entry 10). Therefore, the use of allylSmBr/
HMPA (1∶4) as the SET reagent was proven to be an
efficient approach to realize the transformation of
1
1a
2
2b, 61 (43)
2c, 65 (51)
2d, 77 (65)
2e, 68 (55)
2f, 65 (50)
3b, 35 (45)
3c, 30 (42)
3d, 18 (trace)
3e, 23 (37)
3f, 26 (32)
Me
1b
3
Me
1c
4
MeO
1d
5
MeO
1e
6
OMe
1f
144
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Chin. J. Chem. 2013, 31, 143—148

Reactivity of AllylSmBr/HMPA: Facile Synthesis of 3-Aryl-1,2,4-benzotriazines
To disclose the role of HMPA, the reactivity of allyl-
Continued
Yield of 3b/%
SmBr and allylSmBr/HMPA was further compared by
using an aliphatic gem-dibenzotriazolyl compound 1p as
the substrate (Scheme 2). Interestingly, in the absence of
HMPA, allylSmBr behaved as an organometallic nu-
cleophile and 4p was isolated as the major product ac-
companied by a minor reductive debenzotriazolylation
product 3p. On the other hand, by using HMPA as the
additive, 4p was not detected and 3p became the major
product. These results indicate that by the use of HMPA,
the substitution reaction was significantly suppressed
and the reductive debenzotriazolylation became the
main process.
Entrya Ar of 1
Yield of 2b/%
2g, 52 (29)
7
3g, 31 (60)
3h, 19 (39)
3i, 20 (trace)
3j, 20 (45)
3k, 21 (24)
Cl
1g
1h
1i
8
2h, 70 (56)
2i, 68 (54)
2j, 59 (44)
2k, 45 (25)
Br
9
Br
10
F
1j
11
12
Table 3 Formation of 3-aryl-1,2,4-benzotriazines from 4 with
1k
allylSmBr
Entry Ar, 1'
Yield of 2a/%
2a, nonec
Yield of 2b/%
2a, 45
2a, 33 (0)c
3l, 25 (68)
Cl
1l
1
1'a
2
2b, nonec
2c, nonec
2d, nonec
2b, 48
2c, 43
2d, 42
d
d
13
－
－
MeO
NC
1'b
1m
1n
3
Me
1'c
e
e
14
－
－
O2N
4
Cl
1'd
a Reaction conditions: subtrate 1' (1 mmol), allyl bromide (2.2
mmol), Sm (2.2 mmol), in THF (20mL) at r.t. overnight. Detected
by TLC. b HMPA (8.8 equiv) was used as the additive. Isolated
yields based on 1'. Isolation of 3 was not attempted because of
the trace amount. c No reaction occurred and the starting 1' could
be recovered almost quantitatively.
15
2o, 45
3o, 5
O
1o
a Reaction conditions: substrate 1 (1 mmol), allyl bromide (2.2
mmol), Sm (2.2 mmol), and HMPA (8.8 equiv., 1.5 g) in THF
b
(20 mL) at r.t. for
1
h.
Isolated yields based on
1,l-bis(benzotriazo1-1-yl)methylarenes. The yields in the paren-
theses referred to those obtained with allylSmBr in the absence of
HMPA. c No reductive rearrangement product was detected. d No
reaction. e The reaction is messy.
Unlike bis(benzotrizaol-1-yl)methylarenes 1a－1l,
aliphatic gem-dibenzotriazolyl compound 1p failed to
afford the 1,2,4-benzotriazine (2p). This could be at-
tributed to a highly unstable primary alkyl radical inter-
mediate 1pA, which may abstract hydrogen from THF
preferably thus forming 3p, rather than undergoing the
rearrangement to generate 2p.
To verify the potential radical process, a cyclopropyl
substituent was introduced. The rearrangement of
cyclopropylcarbinyl radical to allylcarbinyl radical has
been used as a free-racidal clock.[13] When compound
1q was treated with allylSm/HMPA, two products 2q
and 3q were obtained in 25% and 30% yield, respec-
tively, along with the isolation of 5q in 9% yield
(Scheme 3).
1-(Benzotriazo1-1-yl)-1-(benzotriazo1-2-yl)methyl-
arenes 1' were always obtained in a considerable
amount during the preparation of 1.[4] Therefore, trans-
formation of 1' into 2 would also be desirable (Scheme
1). However, the treatment of 1' with allylSmBr alone
led to a complete recovery of the starting material (Ta-
ble 3) and failed to afford any desired product. In con-
trast, applying the allylSmBr/HMPA system to 1'a－1'd
resulted in 2a－2d in reasonable yields (Table 3). Al-
though the yields were not as that satisfactory, allyl-
SmBr/HMPA (1∶4) system did show improved reac-
tivity than allylSmBr alone.
Reductive debenzotriazolylation of 1q produced
radical intermediate 1qA, which underwent the ring-
opening of benzotriazolyl and would lead to 2q. How-
ever, 1qA could alternatively underwent the ring-open-
ing of cyclopropyl to generate intermediate 1qB and fi-
nally afforded 5q. The formation of 5q further supports
the free radical mechanism.[12] It was also worth nothing
that the employment of allylSmBr/HMPA afforded 5q,
Scheme 1 Synthesis of 3-aryl-1,2,4-benzotriazines 2 from
1-(benzotriazo1-1-yl)-1-(benzotriazo1-2-yl)methyl arenes 1'
N
SmBr
N
N
N
N
N
N
N
N
Ar
HMPA, THF
H
1'
Ar
2
Chin. J. Chem. 2013, 31, 143—148
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145

Yin et al.
FULL PAPER
Scheme 2 The reactions of aliphatic gem-dibenzotriazolyl compound 1p
N
N
N
N
N
N
N
-
-Bt
N
N
H
4p
SmBr
1p
N
N
N
N
Hydrogen abstraction
SmII
1e.
N
N
H
3p
1pA
N
N
N
N
N
N
N
N
N
-H
H
2p
2p
3p
4p
AllylSmBr
AllylSmBr/HMPA
0%
0%
20% 62%
65% 0%
Scheme 3 The reactions of aliphatic gem-dibenzotriazolyl compound 1q
N
N
N
N
N
N
N
AllylSmBr
-Bt
N
N
H
H
1q
4q
N
N
N
N
N
N
N
N
N
N
-H
SmII
1e.
N
N
H
H
1e.
SmII
2q
1qA
N
N
N
N
N
H abstraction
N
N
N
N
H
1qA
5q
1qB
N
N
H abstraction
2q 3q
AllylSmBr 0% 19% 31% 0%
AllylSmBr/HMPA
4q 5q
N
3q
25% 30% 0% 9%
3q and 2q in 64% overall yield and no allylated product
4q was detected, demonstrating its full reducing reactiv-
ity. While treatment of 1q with allylSmBr alone af-
forded 4q in 31% yield accompanied by minor reductive
debenzotriazoylated product 3q, exhibiting to a large
extent its nucleophilic property.
To further explore the reactivity of allylSmBr/
HMPA, benzotriazole derivative 1r was treated with
allylSmBr/HMPA and a reductive-coupling product 7r
was obtained in high yield (85%, Scheme 4). Instead, 1r
was smoothly substituted by allylSmBr to afford 6r in
74% yield in the absence of HMPA.[2e]
Scheme 4 The reactions of N-((1H-benzo[d][1,2,3]triazol-1-yl)-(phenyl)methyl)benzamide 1r
O
SmBr
N
H
THF
O
Bt
6r,
74%
( ref. 2e)
N
H
O
H
1r
SmBr
N
N
H
O
HMPA, THF
7r, 85%
146
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Chin. J. Chem. 2013, 31, 143—148

Reactivity of AllylSmBr/HMPA: Facile Synthesis of 3-Aryl-1,2,4-benzotriazines
Thus the addition of HMPA not only plays a role in
stabilizing the radical intermediate and enhances the
tendency of radical rearrangement process. It is also
probable to function in switching the nucleophilic allyl-
SmBr into a strong SET reagent by coordinating with
the divalant samarium in allylSmBr. And a structure of
the SmI2(HMPA)4 complex has been characterized by
Hou group[14] using crystallography technology.
ucts 2－5.
3-(4-Methoxyphenyl)benzo[e][1,2,4]triazine (2d)1
1
Orange solid; H NMR (400 MHz, CDCl3) δ: 8.71－
8.74 (m, 2H, ArH), 8.50 (d, J＝8.0 Hz, 1H, ArH), 8.04
(d, J＝8.0 Hz, 1H, ArH), 7.92－7.96 (m, 1H, ArH), 7.76
－7.80 (m, 1H, ArH), 7.10 (d, J＝8.0 Hz, 2H, ArH),
3.93 (s, 3H, OCH3); 13C NMR (100 Hz, CDCl3) δ: 162.5,
159.7, 146.1, 141.2, 135.4, 130.5, 129.6, 129.0, 128.2,
114.4, 110.0, 55.5.
3-(4-Fluorophenyl)benzo[e][1,2,4]triazine
(2j)
Conclusions
1
Yellow solid; H NMR (400 MHz, CDCl3) δ: 8.75－
8.79 (m, 2H, ArH), 8.51－8.54 (m, 1H, ArH), 8.07 (d,
J＝8.0 Hz, 1H, ArH), 7.95－7.99 (m, 1H, ArH), 7.81－
7.85 (m, 1H, ArH), 7.24－7.29 (m, 2H, ArH); 13C NMR
(100 MHz, CDCl3) δ: 166.4, 163.9, 158.9, 146.3, 141.0,
135.6, 131.8, 130.9, 129.6, 116.1, 115.9. HRMS (EI)
calcd for C13H9FN3 [M ＋ H] ＋ : 226.0775, found
226.0782.
(E)-3-Styrylbenzo[e][1,2,4]triazine (2k) Yellow
solid; 1H NMR (400 MHz, CDCl3) δ: 8.51 (d, J＝8.0 Hz,
1H, ArH), 8.42 (m, J＝16.0 Hz, 1H, CH), 8.02 (d, J＝
8.0 Hz, 1H, ArH), 7.94－7.98 (m, 1H, ArH), 7.79－7.83
(m, 1H, ArH), 7.73－7.74 (m, 2H, ArH), 7.63 (d, J＝
16.0 Hz, 1H, CH), 7.40－7.47 (m, 3H, ArH); 13C NMR
(100 MHz, CDCl3) δ: 160.4, 146.0, 141.0, 140.2, 135.9,
135.5 129.9, 129.7, 129.6, 128.9, 128.7, 127.9, 125.1.
HRMS (ESI) calcd for C15H12N3 [M＋H]＋: 234.1026,
found 234.1019.
In conclusion, allylSmBr/HMPA system provided a
facile synthesis of 3-aryl-1,2,4-benzotriazines from the
gem-dibenzotriazolyl compounds. This divalent samar-
ium system based on allylSmBr would be a promising
tool in the reductive reactions. Further investigation
concerning the use of various additives to tune the SET
activity of allylSmBr and more synthetic applications of
the allylSmBr/additive system is currently underway in
this laboratory and will be reported in due course.
Experimental
The NMR spectra were recorded in CDCl3 or
d6-DMSO on a 400 MHz instrument with Me4Si as an
internal standard. Recorded shifts are reported in parts
per million (δ) downfield from TMS. Data are repre-
sented as follows: chemical shift, mutiplicity (s＝singlet,
d＝doublet, t＝triplet, q＝quartet, m＝multiplet, b＝
broad), coupling constant (J, Hz) and integration.
Anlytical TLC was carried out with 0.2 mm thick silica
gel plates (GF254). Visualization was accomplished by
UV light. The columns were hand packed with silica gel
60 (300－400). Compounds 1a－1o and 1'a－1'd were
synthesized according to references.[4] All reagents were
used without further purification after receiving. All
solvents were distilled using the standard procedures.[15]
3-Cyclopropylbenzo[e][1,2,4]triazine
(2q)
Yellow oil; 1H NMR (400 MHz, CDCl3) δ: 7.46 (d, J＝
8.0 Hz, 1H, ArH), 7.69－7.91 (m, 3H, ArH), 2.71－2.73
(m, 1H, CH), 1.43－1.45 (m, 2H, CH2), 1.26－1.32 (m,
2H, CH2); 13C NMR (100 MHz, CDCl3) δ: 167.5, 146.3,
141.0, 135.3, 129.6, 129.2, 128.2, 17.2, 11.9. HRMS
(ESI) calcd for C10H10N3 [M＋H]＋: 172.0869, found
172.0877.
1-(Hept-1-en-4-yl)-1H-benzo[d][1,2,3]triazole (4p)
1
General procedure for the preparation of 3-aryl-
1,2,4-benzotriazines of dibenzotriazolyl compounds
using allylSmBr/HMPA
Brown solid; H NMR (400 MHz, CDCl3) δ: 8.07 (d,
J＝8.0 Hz, 1H, ArH), 7.53 (d, J＝8.0 Hz, 1H, ArH),
7.44－7.48 (m, 1H, ArH), 7.34－7.38 (m, 1H, ArH),
5.55－5.65 (m, 1H, CH＝), 4.90－5.01 (m, 2H,＝CH2),
4.77－4.84 (m, 1H, NCH), 2.88－2.96 (m, 1H), 2.74－
2.80 (m, 1H), 2.21－2.28 (m, 1H), 1.97－2.03 (m, 1H),
1.19－1.23 (m, 2H, CH2), 0.87 (t, J＝6.4 Hz, 3H, CH3);
13C NMR (100 MHz, CDCl3) δ: 133.3, 127.0, 123.8,
120.1, 118.4, 109.6, 60.2, 39.4, 36.5, 19.4, 13.6. HRMS
(ESI) calcd for C13H18N3 [M＋H]＋: 216.1495, found
214.1488.
To a two-necked flask, samarium powder (0.33 g, 2.2
mmol) and allylbromide (0.26 g, 2.2 mmol) in THF (20
mL) were added at r.t. under nitrogen. When the color of
the mixture turned purple, the stirring was continued for
an additional 1 h until the samarium powder disappeared.
Subsequently, HMPA (1.50 g, 8.8 mmol) and the
dibenzotriazolyl compound 1 (1.0 mmol) were added.
The addition of HMPA to the solution of allylSmBr re-
sulted in a deep purple mixture and the color faded
gradually with the reaction (usually in 1 h). Sodium
patassium tartrate (aq. sat., 5 mL) was then added and
the corresponding mixture was extracted with ethyl ace-
tate (10 mL×3). The combined organic layers were
washed with brine (10 mL×2) and dried over anhy-
drous Na2SO4. The organic solvent was removed by
evaporation under reduced pressure. The residue was
subjected to purification by flash column chromatogra-
phy on silca gel (PE∶EA＝6∶1, V∶V) to afford prod-
1-(1-Cyclopropylbut-3-en-1-yl)-1H-benzo[d][1,2,
1
3]triazole (4q) Yellow oil; H NMR (400 MHz,
CDCl3) δ: 8.07 (d, J＝8.0 Hz, 1H, ArH), 7.53 (d, J＝8.0
Hz, 1H, ArH), 7.43－7.47 (m, 1H, ArH), 7.33－7.37
(m , 1H, ArH), 5.60－5.64 (m, 1H, CH＝), 4.90－5.01
(m, 2H,＝CH2), 4.04－4.10 (m, 1H, NCH), 2.94－3.08
(m, 2H, CH2), 1.64－1.66 (m, 1H, CH), 0.79－0.82 (m,
1H), 0.45－0.49 (m, 2H), 0.30－0.32 (m, 1H); 13C
NMR (100 MHz, CDCl3) δ: 133.3, 129.2, 127.0, 123.79,
120.1, 118.3, 109.8, 65.8, 39.3, 15.8, 5.4. HRMS (ESI)
Chin. J. Chem. 2013, 31, 143—148
© 2013 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
147

Yin et al.
FULL PAPER
calcd for C13H16N3 [M＋H]＋: 214.1339, found 214.1346.
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Acknowledgement
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This work was financially supported by National
Natural Science Foundation of China (No. 20802070)
and the research foundation from Key Laboratory of
Synthetic Organic Chemistry of Natural Substances,
Shanghai Institute of Organic Chemistry (CAS). We
thank Professor Ran Hong at SIOC for helpful discus-
sions.
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