Synthesis and NMR spectral studies of the 7-C60-adduct of N,N-(tetrachlorophthaloyl)dehydroabietylamine

Article abstract of DOI:10.3390/molecules17044209

The 7-C₆₀-adduct of N,N-(tetrachlorophthaloyl) dehydroabietylamine was synthesized for the first time and characterized by IR, UV-vis, mass and NMR spectral studies. The ¹H-NMR and ¹³C-NMR resonance signals of the new comp

Full text of DOI:10.3390/molecules17044209

Molecules 2012, 17, 4209-4218; doi:10.3390/molecules17044209
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molecules
ISSN 1420-3049
www.mdpi.com/journal/molecules
Article
Synthesis and NMR Spectral Studies of the 7-C60-Adduct of
N,N-(Tetrachlorophthaloyl)dehydroabietylamine
Zhi Zhou 1,2,* and Zhongxiang Lin 1
1
College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China
2
College of Life and Environmental Sciences, Kaili University, Kaili, Guizhou 556011, China
* Author to whom correspondence should be addressed; E-Mail: zhou86zhi@163.com;
Tel./Fax: +86-25-8542-7065.
Received: 4 March 2012; in revised form: 25 March 2012 / Accepted: 27 March 2012 /
Published: 5 April 2012
Abstract: The 7-C60-adduct of N,N-(tetrachlorophthaloyl)dehydroabietylamine was
synthesized for the first time and characterized by IR, UV-vis, mass and NMR spectral
1
studies. The H-NMR and 13C-NMR resonance signals of the new compound are
unambiguously assigned by using homo- and heteronuclear 2D NMR spectroscopic
techniques such as COSY, ROESY, HSQC and HMBC. The C1 symmetric structure with
6,6-junction of compound was determined.
1
Keywords: 7-C60-adduct of N,N-(tetrachlorophthaloyl)dehydroabietylamine; H-NMR;
13C-NMR; 2D NMR; C1 symmetric structure
1. Introduction
Dehydroabietylamine, which possesses an aromatic diterpene structure with three rings and a
reactive amino group and is the main component of disproportionated rosin amine, can be easily
isolated from the latter. Dehydroabietylamine and its derivatives have attracted considerable interest
due to their wide range of uses such as chiral resolution agents [1,2], antibacterial substances [3,4] and
chiral surfactants [5,6].
Since the discovery of C60, its peculiar cage structure has attracted great attention. Cycloaddition
reactions of C60, especially 1,3-dipolar addition reactions, have been the subject of a large variety of
studies and shown to be a useful methods for the synthesis of functionalized fullerene derivatives [7–11].
These results prompted us to study new cycloadducts of dehydroabietylamine with C60 as a part of an

Molecules 2012, 17
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on-going program for the development of new rosin amine derivatives with potential biological or
material properties. So far, the majority of the studies on the chemical transformations of
dehydroabietylamine have focused on the amine group and benzene ring, but the chemical
transformation in other skeleton has seldom been reported. In this paper, we report the synthesis for the
first time of the 7-C60-adduct of N,N-(tetrachlorophthaloyl)dehydroabietylamine (5, Figure 1) and
1
13
describe the structure determination of the new compound, along with its detailed H- and C-NMR
assignments.
Figure 1. Chemical structure of 7-C60-adduct of N,N-(tetrachlorophthaloyl)dehydroabietylamine (5).
16
12
15
11
9
20
5
17
13
14
1
2
10
4
8
3
7
19
6
22
21
18
8'
O
O
7'
N
6'
5'
Cl
Cl
1'
4'
2'
Cl
3'
Cl
2. Results and Discussion
2.1. Synthesis Procedures
The general procedure for the synthesis of compound 5 is shown in Scheme 1.
Dehydroabietylamine (1) was prepared as described in the literature [12]. Dehydroabietylamine
reacted with tetrachlorophthalic anhydride (TCPA, an amino protecting group) to give compound 2,
which then was transformed into 3 by C-7 benzylic oxidation. Subsequently, the reaction of 3 with
p-tosylhydrazide yielded p-tosylhydrazone 4. Compound 5 was prepared according to the reported
method [13]. According to the literature [13], heating a solution of the p-tosylhydrazone with C60 at
70 °C afford the [5,6]-open isomer. However, in our experiment, no traces of this expected [5,6]-open
isomer were found and the only isolated product was the [6,6]-closed isomer (methanofullerene),
which is likely due to a rearrangement of the 5,6-open isomer into the thermodynamically more stable
6,6-closed isomer at 70 °C.
2.2. Analysis of Compound 5
2.2.1. IR, UV-Vis and Mass Spectrum Analysis of Compound 5
The IR spectrum of compound 5 showed bands indicating the presence of the different expected
functional groups: Characteristic asymmetric and symmetric stretching bands of the imide carbonyl
(C=O) at 1,776 and 1,721 cm−1 and at 526 cm−1 for the C60 skeleton. In the UV-vis spectrum, the
characteristic absorptions for the methanofullerenes was also observed at 436.50, 697.00 nm [13].
Meanwhile, the structure of compound 5 as a monoadduct was supported by the matrix-assisted laser

Molecules 2012, 17
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desorption/ionization time of flight mass spectrum (MALDI-TOF MS) which display the expected
peak at m/z 1,271.4.
Scheme 1. Preparation of compound 5.
(i)
(ii)
(iii)
O
NNHTs
H2N
R
R
R
3
2
1
4
(iv)
Cl
Cl
O
Cl
Cl
R
N
=
R
O
5
Reagents and conditions: (i) TCPA, acetic acid, N2, 135 °C, 2.5 h; (ii) 65% t-BuOOH, CrO3 (cat.),
pyridine, CH2Cl2, rt, 24 h; (iii) TsNHNH2, PTSA (cat.), benzene-EtOH (4:1), reflux, 8 h; (iv)
NaOMe, pyridine, 15 min, rt; then C60 in chlorobenzene, N2, 70 °C, 24 h.
2.2.2. 1H-NMR Spectrum Analysis of Compound 5
The 1H-, 13C-NMR and 2D NMR spectra for compound 5 are summarized in Table 1.
Table 1. 1H- and 13C-NMR data, 1H-1H correlations in COSY, ROESY spectra and 1H-13C
correlations in HSQC, HMBC spectra for compound 5.
C
δC (ppm)
H
δH (ppm)
HSQC
HMBC
COSY
H-1α, 2
H-1β, 2
ROESY
1
39.48
1β
1α
2
2.39 (br d, J = 11.9 Hz)
1.79–1.74 (m)
1.85–1.79 (m, 2H)
1.58 (br d, J = 13.0 Hz)
1.53–1.47 (m)
―
H-1β, 1α
H-20, 2, 3α
H-20, 11, 2, 1α
H-5, 11, 1β
2
3
18.18
37.52
H-2
H-3β, 3α, 1β, 1α H-19, 3β, 3α, 1β
3β
3α
―
H-3β, 3α
H-19, 18α, 18β
H-3α, 2
H-3β, 2
―
H-19, 3α, 2
H-5, 18α, 3β, 2
―
4
5
6
40.89
48.67
28.35
―
H-19, 5, 18α,
18β, 6β
5
1.97 (dd, J = 10.3, 9.2 Hz)
H-5
H-19, 20, 18α, H-6β, 6α
18β, 6α, 6β
H-3α, 1α, 6α,
18α, 2
6β
6α
―
―
―
3.65 (dd, J = 14.1, 10.5 Hz)
H-6β, 6α
C-6/H-5
H-5, 6α
H-5, 6β
―
H-19, 20, 6α
3.41 (dd, J = 14.1, 8.8 Hz)
H-5, 6β, 18α
7
8
9
44.61
―
―
―
―
―
―
H-6α, 6β, 14, 11
H-6β, 11,
―
―
―
132.15
150.35
―
H-14, 12, 20, 5
―

Molecules 2012, 17
4212
Table 1. Cont.
C
δC (ppm)
H
δH (ppm)
HSQC
HMBC
COSY
ROESY
10
38.83
―
―
―
H-20, 5, 6α, 2,
11
―
―
11
12
13
14
15
16
17
18
123.40
126.09
145.43
126.42
33.92
11
7.43 (d, J = 8.1 Hz)
7.28 (dd, J = 8.1, 1.8 Hz)
―
H-11
H-12
―
H-12
H-12
H-11
―
H-1β, 1α, 12
H-15, 11, 16
―
12
H-15, 11, 14
H-16, 17, 15, 11
H-12, 15
―
14
8.40 (d, J = 1.8 Hz)
2.99 (septet, J = 6.7 Hz)
1.30 (d, J = 6.8 Hz, 3H)
1.32 (d, J = 7.0 Hz, 3H)
3.88 (d, J = 13.6 Hz)
3.59 (d, J = 13.6 Hz)
1.31 (s, 3H)
H-14
H-15
H-16
H-17
H-18β, 18α
―
―
15
H-16, 17, 12, 14 H-16, 17
H-16, 17, 12
H-15, 12
H-15
23.70
16
H-15, 17,
H-15, 16
H-19, 5
H-15
H-15
H-18α
H-18β
―
24.49
17
50.45
18β
18α
19
H-18α, 19
H-18β, 5, 3α, 6α
19
18.89
H-19
H-5, 18α, 18β
H-20, 6β, 18β,
3β, 2
20
22.50
20
―
―
―
―
―
―
―
1.86 (s, 3H)
H-20
―
H-1α, 5
H-6α, 6β
H-6α
―
―
―
―
―
―
―
―
―
H-19, 6β, 1β
21,22
84.80
―
―
―
―
―
―
―
―
―
―
―
―
―
―
77.66
―
1',6'
2',5'
3',4'
7',8'
C60
127.52
129.76
140.35
164.51
150.74–
137.82
―
―
―
―
―
―
H-18α, 18β
―
―
1
First, the assignment of some protons is easily accomplished by analysis of the H-NMR chemical
shifts, signal multiplicity and coupling constants. The signals of the aromatic protons (7.26–8.40 ppm)
can be readily identified by their chemical environment (Figure 2).
Figure 2. 1H-NMR spectrum of compound 5.

Molecules 2012, 17
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The H-11 signal appeared as a doublet with coupling constants J11,12 = 8.1 Hz at 7.43 ppm, while
the H-14 signal appeared at 8.40 ppm as a doublet with a lower coupling constant values J14,12 = 1.8 Hz
because of the long distance between H-14 and H-12. H-12 signal appeared as a double doublet with
J
12,11 = 8.1 and J12,14 = 1.8 Hz at 7.28 ppm. The septet at 2.99 ppm (J = 6.7 Hz) was assigned to H-15
proton. In the higher frequency region there are three double doublets and two doublets at δH 3.65 (dd,
J = 14.1, 10.5 Hz), 3.41 (dd, J = 14.1, 8.8 Hz) 1.97 (dd, J = 10.3, 9.2 Hz), 3.88 (d, J = 13.6 Hz) and
3.59 ppm (d, J = 13.6 Hz). Of the five signals, δH 3.88 and 3.59 ppm doublets were assigned to H-18
(H-18β and H-18α) on the basis of the correlations of δC 50.45 ppm/H-18β, 18α in the HSQC spectrum,
while δH 3.65 and 3.41 ppm double doublets were assigned to the H-6 (H-6β and H-6α) on the basis of
the correlations of δC 28.35 ppm/H-6β, 6α in the HSQC spectrum. The remaining double doublet at δH
1.97 ppm was assigned to H-5. To distinguish the non-equivalent H-18 and H-6 protons, we found that
δH 3.59 and 3.41 ppm showed ROE correlations with H-5, but δH 3.88 and 3.65 ppm showed no ROE
correlations with H-5 in the ROESY spectrum. Therefore, we assigned H-18α at δ 3.59, H-6α at δ 3.41,
H-18β at δ 3.88 and H-6β at δ 3.65 ppm.
The signals of four-methyl group protons appeared as two singlets and two doublets. The two
singlets, one at δH 1.86 ppm was assigned to H-20 methyl protons, and the other at δH 1.31 ppm was
assigned to H-19 methyl protons based on the correlations of δH 1.86/H-19, 6β and δH 1.31/H-20, 6β,
18β in the ROESY spectrum. The doublet at δH 1.30 ppm was readily assigned to H-16 methyl protons
in the isopropyl moiety due to the δH 1.30/H-15 correlation in the COSY spectrum and δH 1.30/H-15,
12 correlations in the ROESY spectrum. The remaining doublet at δH 1.32 ppm was assigned to H-17
methyl protons.
Finally, the signals of the remaining three-methylene group protons (H-1, 2, 3) appeared as two
broad doublets and three multiplets. The broad doublet at δH 2.39 ppm and the multiplet at
δH 1.79–1.74 ppm were, respectively, assigned to H-1β and H-1α due to the correlations of
δH 2.39/1.79–1.74/δC 39.48 ppm in the HSQC spectrum and δH 2.39/H-20, 11, δH 1.79–1.74/H-5, 11 in
the ROESY spectrum. Similarly, the broad doublet at δH 1.58 ppm and the multiplet at δH 1.53–1.47 ppm
were, respectively, assigned to H-3β and H-3α based on the correlations of δH 1.58/1.53–1.47/δC 37.52 ppm
in the HSQC spectrum and δH 1.58/H-19, δH 1.53–1.47/H-5, 18α in the ROESY spectrum. The
remaining multiplet at δH 1.85–1.79 ppm was assigned to H-2, which also be demonstrated by the
correlations of δH 1.85–1.79/H-3β, 3α, 1β, 1α in the COSY spectrum.
2.2.3. 13C-NMR Spectrum Analysis of Compound 5
13
The proton noise decoupled C-NMR spectrum (Figure 3) displayed 24 and 43 resonance signals
respectively for (tetrachlorophthaloyl)dehydroabietylamine moiety and C60 moiety of compound 5.
In the 13C-NMR spectrum, the signal at δC 164.51 ppm could be assigned to C-7', 8', which was
supported by the cross peaks of δC 164.51 ppm/H-18α, 18β in the HMBC spectrum.
In the HSQC spectrum, the signals at δC 23.70, 24.49, 18.89 and 22.50 ppm were attributed to C-16,
17, 19, 20 methyl carbon atoms due to the cross peaks of δC 23.70/H-16, δC 24.49/H-17, δC 18.89/H-19
and δC 22.50/H-20. In addition, the signals at δC 18.18, 39.48, 37.52, 28.35 and 50.45 ppm were
attributed to C-2, 1, 3, 6, 18 methylene carbon atoms due to the cross peaks of δC 18.18/H-2,
δC 39.48/H-1α,1β, δC 37.52/ H-3α, 3β, δC 28.35/H-6α, 6β and δC 50.45/H-18α, 18β. The resonance

Molecules 2012, 17
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signals at δC 48.67 and 33.92 ppm were assigned to methine carbon atoms C-5 and C-15 based on the
cross peaks of δC 48.67/H-5 and δC 33.92/H-15. The HSQC spectrum also revealed the cross peaks
between aromatic hydrogens H-11, 12, 14 and their corresponding carbon atoms. From the HSQC
spectrum, we can clearly assign C-11 at δC 123.40, C-12 at δC 126.09 and C-14 at δC 126.42 ppm.
Figure 3. 13C-NMR spectrum of compound 5.
The quaternary carbon atoms were assigned by using the long-range correlated HMBC experiment.
The signals at δC 40.89, 132.15, 150.35, 38.83 and 145.43 ppm were assigned to C-4, 8, 9, 10, 13
quaternary carbon atoms because of the long-range cross peaks of δC 40.89 ppm/H-19, 5, 18α, 18β, 6β,
δC 132.15 ppm/H-6β, 11, δC 150.35 ppm/H-14, 12, 20, 5, δC 38.83 ppm/H-20, 5, 6α, 2, 11 and
δC 145.43 ppm/H-16, 17, 15, 11. The signals at δC 44.61, 84.80, 77.66 ppm were assigned to C-7 and
the sp3-hybridized bridgehead carbon atom C-21, 22 on the cyclopropyl moiety due to the long-range
cross peaks of δC 44.61 ppm/H-6α, 6β, 14, 11, δC 84.80 ppm/H-6α, 6β and δC 77.66 ppm/H-6α. This
pattern is unambiguously diagnostic for C1 symmetric structure with 6,6-junction [14,15].
Only four signals were observed in the tetrachlorophthaloyl moiety due to the symmetry of C-7', 8',
C-1', 6', C-2', 5' and C-3', 4'. The carbon signals at δC 127.52, 129.76, 140.35 ppm can be assigned to
C-1', 6', C-2', 5' and C-3', 4' [16]. The remaining 41 resonance signals between δC 150.74–137.82 ppm
were attributed to C60-sp2 carbon atoms (due to the overlapping, only 41 resonance signals for C60-sp2
carbon atoms were observed, maximum 58 sp2-carbon resonance signals).

Molecules 2012, 17
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3. Experimental
3.1. General
1D (1H and 13C) and 2D NMR experiments were performed on a Bruker AVANCE AV-500 NMR
1
13
spectrometer (500.13 MHz for H and 125.77 MHz for C). The samples were dissolved in 0.5 mL
1
13
CDCl3, H-NMR and C-NMR spectra were recorded using TMS as an internal reference. Chemical
shifts were reported in parts per million (ppm). FT infrared (IR) spectrum were recorded as KBr pellets
on a Nicolet 360 FT-IR spectrometer and UV-vis spectra on a Shimadzu UV-2550 UV-VIS
spectrometer. ESI mass spectrometric were obtained on Agilent 1100 Capillary LC/Micromass Q-Tof
Micro mass spectrometer. Matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF)
mass spectra was performed on a Bruker Daltonics Autoflex III mass spectrometer using α-cyano-4-
hydroxycinnamic acid (CHCA) as a matrix in a negative-ion reflector mode. All chemicals and
solvents were obtained from commercial sources and used as received or dried according to standard
procedures. Column chromatography was performed on silica gel (ZCXⅡ, 100–200 mesh). Chemical
reactions were monitored by thin layer chromatography using precoated silica gel GF254 plates.
3.2. Preparation of N,N-(Tetrachlorophthaloyl)dehydroabietylamine (2)
A mixture of tetrachlorophthalic anhydride (5 g, 17.5 mmol), dehydroabietylamine (5 g, 17.5 mmol),
and glacial acetic acid (60 mL) was stirred under N2 at 135 °C for 2.5 h. Then the mixture was cooled
and poured into 250 mL of ice water. The solid was filtered, washed successively with distilled water
and ethanol, dried in vacuo to give the crude product, which was purified by column chromatography
on silica gel (petroleum ether-toluene, 2:1) to yield 2 as a white solid (7.11 g, 73.4%), m.p. 220–221 °C.
IR νmax/cm–1: 2934, 2860, 1776, 1714, 1630, 1498, 1430, 1392, 1369, 1338, 1297, 1200, 1091, 1069,
879, 820, 736, 556, 476; 1H-NMR: δ 7.13 (d, J = 7.9 Hz, 1H), 6.96 (dd, J = 8.2, 1.5 Hz, 1H), 6.91 (s,
1H), 3.68 (d, J = 13.7 Hz, 1H), 3.55 (d, J = 13.7 Hz, 1H), 2.98–2.96 (m, 2H), 2.81 (septet, J = 6.9 Hz,
1H), 2.26 (br d, J = 12.5 Hz, 1H), 2.22–2.18 (m, 1H), 1.86–1.79 (m, 1H), 1.75–1.62 (m, 2H), 1.49 (dd,
J = 13.4, 1.2 Hz, 1H), 1.44–1.28 (m, 3H, H-1α), 1.23 (s, 3H), 1.21 (d, J = 7.0 Hz, 6H), 1.05 (s, 3H);
13C-NMR: δ 164.50 (2C=O, imide), 147.09, 145.69, 140.07 (2C, -N(CO)2C6Cl4), 134.86, 129.58 (2C,
-N(CO)2C6Cl4), 127.52 (2C, -N(CO)2C6Cl4), 127.05, 123.82, 123.78, 49.89, 45.39, 39.53, 38.09,
37.61, 37.21, 33.44, 30.07, 25.81, 23.96, 23.94, 19.45, 19.06, 18.45; TOF MS (ES−) m/z 524.3
37
37
([M(35Cl4)–C2H3]−), 526.2 ([M(35Cl3 Cl)–C2H3]−), 528.2 ([M(35Cl2 Cl2)–C2H3]−). Anal. Calcd for
C28H29Cl4NO2 (553.3): C, 60.78; H, 5.28; N, 2.53. Found: C, 60.37; H, 5.35; N, 2.48.
3.3. Preparation of 7-oxo-N,N-(Tetrachlorophthaloyl)dehydroabietylamine (3)
To a mixture of CrO3 (45 mg, 0.45 mmol) and CH2Cl2 (90 mL), 65% t-BuOOH (11.6 mL, 72.3 mmol)
and pyridine (0.073 mL, 0.904 mmol) were added. After stirring at room temperature for 3 min,
compound 2 (5 g, 9.035 mmol) was added. Stirring continued at room temperature for 24 h, the
mixture was concentrated to about 15 mL in vacuo at 30 °C, then poured into methanol (60 mL). The
precipitate formed was filtered and washed with methanol to give a crude product, which was purified
by column chromatography on silica gel (toluene-ethyl acetate, 20:0.5) to afford compound 3 as a

Molecules 2012, 17
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white solid (3.51 g, 68.5%), m.p. 224–226 °C. IR νmax/cm–1: 2961, 2930, 2865, 1777, 1716, 1684, 1608,
1561, 1515, 1489, 1456, 1430, 1377, 1342, 1297, 1248, 1197, 1093, 977, 912, 831, 797, 738, 613, 558,
500, 471; 1H-NMR: δ 7.89 (d, J = 2.1 Hz, 1H), 7.39 (dd, J = 8.1, 2.0 Hz, 1H), 7.27 (d, J = 7.3 Hz, 1H),
3.64 (d, J = 13.7 Hz, 1H), 3.51 (d, J = 13.7 Hz, 1H), 3.06 (dd, J = 18.0, 3.7 Hz, 1H), 2.93 (septet,
J = 6.9 Hz, 1H), 2.76 (dd, J = 18.0, 14.0 Hz, 1H), 2.32 (br d, J = 12.8 Hz, 1H), 2.00 (dd, J = 13.9, 3.5 Hz,
1H), 1.75–1.70 (m, 2H), 1.60–1.48 (m, 2H), 1.45–1.34 (m, 1H), 1.28 (s, 3H), 1.25 (d, J = 7.0 Hz, 6H),
1.12 (s, 3H); 13C-NMR: δ 198.61 (C=O), 164.34 (2C=O, imide), 153.18, 146.89, 140.06 (2C,
-N(CO)2C6Cl4), 132.48, 130.66, 129.60 (2C, -N(CO)2C6Cl4), 127.44 (2C, -N(CO)2C6Cl4), 125.18,
123.34, 49.71, 45.36, 39.16, 37.86, 37.29, 36.82, 36.34, 33.58, 24.18, 23.81, 18.72, 18.00; TOF MS
37
37
(ES+) m/z 565.9 [M(35Cl4)+H]+, 567.9 [M(35Cl3 Cl)+H]+, 569.9 [M(35Cl2 Cl2)+H]+, 571.9
[M(35Cl37Cl3)+H]+, 573.9 [M(37Cl4)+H]+; Anal. Calcd for C28H27Cl4NO3 (567.3): C, 59.28; H, 4.80; N,
2.47. Found: C, 57.66; H, 4.95; N, 2.31.
3.4. Preparation of N,N-(Tetrachlorophthaloyl)dehydroabietylamine p-Tosylhydrazone (4)
To a solution of compound 3 (3 g, 5.288 mmol) in benzene (120 mL) and ethanol (30 mL),
p-toluenesulfonyl hydrazide (1.65 g, 8.86 mmol) and p-toluenesulfonic acid (82 mg, 0.476 mmol) were
added. The reaction mixture was stirred and refluxed during 8 h under N2. After cooling to room
temperature, the mixture was concentrated under vacuum, cooled in an ice bath and the precipitate was
collected by filtration, and washed with ethanol. The crude product was purified by column
chromatography on silica gel (toluene-ethyl acetate, 20:0.4) to yield 4 as a white solid (3.41 g, 87.8%),
m.p. 218–220 °C. IR νmax/cm–1: 3224, 3065, 2927, 2860, 1779, 1719, 1595, 1489, 1433, 1380, 1329,
1
1199, 1163, 1086, 1017, 978, 914, 810, 737, 708, 664, 631, 574, 541, 498, 468; H-NMR: δ 8.08 (s,
1H, NH), 8.02 (d, J = 8.4 Hz, 2H, o-HArSO2-), 7.79 (d, J = 1.8 Hz, 1H), 7.33 (d, J = 8.1 Hz, 2H,
m-HArSO2-), 7.14 (dd, J = 8.1, 1.9 Hz, 1H), 7.10 (d, J = 8.2 Hz, 1H), 3.61 (d, J = 14.1 Hz, 1H), 3.50
(d, J = 14.1 Hz, 1H), 3.15 (dd, J = 17.3, 4.1 Hz, 1H), 2.87 (septet, J = 6.9 Hz, 1H), 2.43 (s, 3H,
CH3ArSO2-), 2.40 (dd, J = 17.2, 13.4 Hz, 1H), 2.21 (br d, J = 12.5 Hz, 1H), 1.73–1.63 (m, 4H), 1.51
(dd, J = 13.3, 3.9 Hz, 1H), 1.44–1.35 (m, 1H), 1.24 (d, 3H, J = 6.9 Hz), 1.23 (d, 3H, J = 6.9 Hz), 1.14
(s, 3H), 1.08 (s, 3H); 13C-NMR: δ 164.46 (2C=O, imide), 153.38 (C=N), 148.89, 146.25, 143.90
(p-ArSO2-), 140.15 (2C, -N(CO)2C6Cl4), 135.69 (p-ArCH3), 129.77, 129.64 (2C, -N(CO)2C6Cl4),
129.42 (2C, m-ArSO2-), 128.51, 128.42 (2C, o-ArSO2-), 127.34 (2C, -N(CO)2C6Cl4), 123.09, 122.61,
49.36, 42.78, 39.44, 37.28, 37.27, 37.11, 33.53, 23.90, 23.72, 23.63, 21.58 (CH3ArSO2-), 19.03, 18.02;
37
37
TOF MS (ES+) m/z 733.9 ([M(35Cl4)+H]+), 735.9 ([M(35Cl3 Cl)+H]+), 737.9 ([M(35Cl2 Cl2)+H]+),
739.9 ([M(35Cl37Cl3)+H]+). Anal. Calcd for C35H35Cl4N3O4S (735.5): C, 57.15; H, 4.80; N, 5.71.
Found: C, 57.53; H, 4.71; N, 5.86.
3.5. Preparation of 7-C60-Adduct of N,N-(Tetrachlorophthaloyl)dehydroabietylamine (5)
Compound 4 (408.9 mg, 0.556 mmol) was dissolved in dry pyridine (7 mL) in a dried three-necked
flask under N2. Then, NaOMe (31.2 mg, 0.578 mmol) was added, and the mixture was stirred for 15 min
at room temperature. A solution of C60 (200 mg, 0.278 mmol) in chlorobenzene (55 mL) was added
and the mixture was stirred at 70 °C for 24 h. After cooling to room temperature the solvent was
evaporated in vacuo, the residue was column chromatographed on silica gel, pre-eluted with CS2 to

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remove unreacted C60 (67.7 mg) and then with CS2-CHCl3 (10:1) to give 5 as a dark brown solid
(145 mg, 41%). IR νmax/cm−1: 3430, 2923, 2858, 1776, 1721, 1628, 1559, 1514, 1459, 1427, 1372,
1334, 1163, 1059, 893, 825, 740, 555, 526, 472; UV-vis (CHCl3) λmax (nm): 697.00, 493.00, 436.50;
1H-NMR: δ 8.40 (d, J = 1.8 Hz, 1H), 7.43 (d, J = 8.1 Hz, 1H), 7.28 (dd, J = 8.1, 1.8 Hz, 1H), 3.88 (d,
J = 13.6 Hz, 1H), 3.65 (dd, J = 14.1, 10.5 Hz, 1H), 3.59 (d, J = 13.6 Hz, 1H), 2.99 (septet, J = 6.7 Hz,
1H), 2.39 (br d, J = 11.9 Hz, 1H), 1.97 (dd, J = 10.3, 9.2 Hz, 1H), 1.86 (s, 3H), 1.85–1.79 (m, 2H),
1.79–1.74 (m, 1H), 1.58 (br d, J = 13.0 Hz, 1H), 1.53–1.47 (m, 1H), 1.32 (d, J = 7.0 Hz, 3H), 1.31 (s, 3H),
1.30 (d, J = 6.8 Hz, 3H); 13C-NMR: δ 164.51 (2C=O, imide), 150.74, 150.35, 149.89, 147.97, 147.53,
145.99, 145.92, 145.43, 145.27, 145.24, 145.21, 145.17, 145.02, 144.96, 144.89, 144.78, 144.68,
144.21, 144.19, 143.97, 143.87, 143.68, 143.25, 143.19, 143.16, 143.06, 143.01, 142.84, 142.76,
142.24, 142.18, 142.13, 142.06, 141.87, 141.40, 141.15, 141.04, 140.84, 140.35 (2C,
-N(CO)2C6Cl4), 140.22, 138.59, 138.51, 137.94, 137.82, 132.15, 129.76 (2C, -N(CO)2C6Cl4), 127.52
(2C, -N(CO)2C6Cl4), 126.42, 126.09, 123.40, 84.80, 77.66, 50.45, 48.67, 44.61, 40.89, 39.48, 38.83,
37.52, 33.92, 28.35, 24.49, 23.70, 22.50, 18.89, 18.18; MALDI-TOF MS (matrix: CHCA, reflectron
37
37
negative) m/z 1269.4 M−(35Cl4), 1271.4 M−(35Cl3 Cl), 1273.4 M−(35Cl2 Cl2), 1275.4 M−(35Cl37Cl3);
Anal. Calcd for C88H27Cl4NO2 (1271.97): C, 83.09; H, 2.14; N, 1.10. Found: C, 82.48; H, 2.20; N, 1.04.
4. Conclusions
In conclusion, the new compound 5 was synthesized from dehydroabietylamine, the assignments of
the proton and carbon signals for 7-C60-adduct of N,N-(tetrachlorophthaloyl)dehydroabietylamine were
made possible by using 1D and 2D NMR techniques including 1H-, 13C-NMR, COSY, ROESY, HSQC
and HMBC experiments. The two peaks at δC 84.80, 77.66 ppm in the 13C-NMR spectra correspond to
the sp3-hybridized bridgehead carbons on the cyclopropyl moiety. This pattern is unambiguously
diagnostic for C1 symmetric structure with 6,6-junction. All the spectral data support and confirm the
proposed structure of the target compound.
Acknowledgments
The authors wish to thank the financial support of the National Natural Science Foundation of China
(No. 30871989).
References and Notes
1. Bolchi, C.; Pallavicini, M.; Fumagalli, L.; Rusconi, C.; Binda, M.; Valoti, E. Resolution of
2-substituted 1,4-benzodioxanes by entrainment. Tetrahedron Asymmetry 2007, 18, 1038–1041.
2. Bolchi, C.; Fumagalli, L.; Moroni, B.; Pallavicini, M.; Valoti, E. A short entry to enantiopure
2-substituted 1,4-benzodioxanes by efficient resolution methods. Tetrahedron Asymmetry 2003,
14, 3779–3785.
3. Wilkerson, W.W.; Galbraith, W.; Delucca, I. Topical antiinflammatory dehydroabietymine
derivatives. IV. Bioorg. Med. Chem. Lett. 1993, 3, 2087–2092.
4. Wilkerson, W.W.; Delucca, I.; Galbraith, W.; Gans, K.; Harris, R.; Jaffee, B.; Kerr, J.
Antiinflammatory phospholipase-A2 inhibitors. I. Eur. J. Med. Chem. 1991, 26, 667–676.

Molecules 2012, 17
4218
5. Wang, Y.; Song, Z.Q. Synthesis of zwitterionic surface active agents from dehydroabietic amine
and correlation between their structures and performance. Chem. Ind. For. Prod. 1996, 16, 1–6.
6. Wang, Y.; Song, Z.Q.; Liang, M.L. Synthesis and characteristics of quaternary ammonium
cationic surfactants from N-dehydroabietyl-N,N-bis(hydroxyethyl)amine. Chem. Ind. For. Prod.
1997, 17, 6–10.
7. Friedman, S.H.; DeCamp, D.L.; Sijbesma, R.P.; Srdanov, G.; Wudl, F.; Kenyon, G.L. Inhibition
of the HIV-1 protease by fullerene derivatives: Model building studies and experimental
verification. J. Am. Chem. Soc. 1993, 115, 6506–6509.
8. Zhao, G.J.; He, Y.J.; Xu, Z.; Hou, J.H.; Zhang, M.J.; Min, J.; Chen, H.Y.; Ye, M.F.; Hong, Z.R.;
Yang, Y.; et al. Effect of carbon chain length in the substituent of PCBM-like molecules on their
photovoltaic properties. Adv. Funct. Mater. 2010, 20, 1480–1487.
9. Sánchez, L.; Rispens, M.T.; Hummelen, J.C. A supramolecular array of fullerenes by quadruple
hydrogen bonding. Angew. Chem. Weinheim Bergstr. Ger. 2002, 41, 838–840.
10. Li, W.S.; Yamamoto, Y.; Fukushima, T.; Saeki, A.; Seki, S.; Tagawa, S.; Masunaga, H.; Sasaki, S.;
Takata, M.; Aida, T. Amphiphilic molecular design as a rational strategy for tailoring bicontinuous
electron donor and acceptor arrays: Photoconductive liquid crystalline oligothiophene-C60 dyads.
J. Am. Chem. Soc. 2008, 130, 8886–8887.
11. Gómez, R.; Segura, J.L. Synthesis of a π-conjugated oligomer-fullerene dyad through a versatile
[6,6] diphenylmethanofullerene carboxylic acid. Tetrahedron 2009, 65, 540–546.
12. Wang, D.L.; Niu, Z.M.; Liu, H.D. Purification and characterization of optically active resolving
reagent dehydroabietylamine. Beijing Ligong Daxue Xuebao 2004, 24, 357–359.
13. Hummelen, J.C.; Knight, B.W.; LePeq, F.; Wudl, F.; Yao, J.; Wilkins, C.L. Preparation and
characterization of fulleroid and methanofullerene derivatives. J. Org. Chem. 1995, 60, 532–538.
14. Liu, S.Z.; Tang, G.S. Symmetry, Cage Structure of [60]Fullerene Derivatives and 13C-NMR
Spectroscopy (in Chinese). Prog. Chem. 2004, 16, 561–573.
15. Khalilov, L.M.; Tulyabaev, A.R.; Tuktarov, A.R. Homo- and methano[60]fullerenes with chiral
attached moieties—1H and 13C-NMR chemical shift assignments and diastereotopicity effects.
Magn. Reson. Chem. 2011, 49, 768–774.
16. Li, Z.J.; Zhang, S.N.; Cui, J.R.; Li, S.C.; Li, Q.; Huang, H.Q.; Cai, M.S. Glycosyl phthalic imidine
compounds with anti-inflammatory activity (in Chinese). C.N. Patent 1,594,342A, 2005.
Sample Availability: Samples of the compounds 2–5 are available from the authors.
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