Synthesis and crystal structure of 2-acetylnaphthalen-6-yl 4-methylbenzosulfonate

Article abstract of DOI:10.1007/s10870-005-4324-8

The title compound has been synthesized by the reaction of 1-(6-hydroxy-2-naphthyl)-1-ethanone (2) with p-toluenesulfonyl chloride. Its structure was determined by single crystal X-ray diffraction. 2-Acetylnaphthalen-6-yl 4-methylbenzosulfonate (3) crystallizes in the orthorhombic space group Pbca with a = 12.727(3) A, b = 14.560 (3) A, c = 17.688 (4) A, V = 3277.8 (11) A³, and Z = 8. The results demonstrate that the dihedral angle between the benzene ring and the naphthalene ring is 116.5°, and the length (1.417 A) of single C - O bond of 3 is longer than that of single C - O bond in the relative compounds.

Full text of DOI:10.1007/s10870-005-4324-8

ꢀC
Journal of Chemical Crystallography, Vol. 35, No. 10, October 2005 ( 2005)
DOI: 10.1007/s10870-005-4324-8
Synthesis and crystal structure of 2-acetylnaphthalen-6-yl
4-methylbenzosulfonate
Li Jia-Rong(1)∗ and Zhang Guang(1)
Received October 28, 2004; accepted March 18, 2005
The title compound has been synthesized by the reaction of 1-(6-hydroxy-2- naphthyl)-
1-ethanone (2) with p-toluenesulfonyl chloride. Its structure was determined by single
crystal X-ray diffraction. 2-Acetylnaphthalen-6-yl 4-methylbenzosulfonate (3) crystal-
˚
˚
lizes in the orthorhombic space group Pbca with a = 12.727(3) A, b = 14.560(3) A,
3
˚
˚
c = 17.688(4) A, V = 3277.8(11) A , and Z = 8. The results demonstrate that the dihe-
dral angle between the benzene ring and the naphthalene ring is 116.5◦, and the length
˚
---
---
(1.417 A) of single C O bond of 3 is longer than that of single C O bond in the relative
compounds.
KEY WORDS: Synthesis; crystal structure; 2-acetylnaphthalen-6-yl 4-methylbenzosulfonate.
Introduction
Experimental
1-(6-Hydroxy-2-naphthyl)-1-ethanone (2) is
The melting point was determined with
XT4A micromelting point apparatus and was un-
corrected. Infrared spectra were recorded with a
Nicolex FT-IR-400 spectrometer. 1H NMR spec-
tra were recorded with RX400 instrument, tetram-
ethylsilane being used as internal standard. Ele-
mental analyses were performed by using the flash
EA112 method. MS were recorded with ZAB-HS
instrument using the EI method.
an important intermediate for the preparation of
naproxen, an anti-inflammatory drug, and for
the synthesis of 2-(1-{6-[(2-[18F]fluoroethyl)
(methyl)-amino]-2-naphthyl}ethylidene)malono-
nitrile ([18F]FDDNP) which is a promising imag-
ing agent in the early diagnosis of Alzheimer’s
disease.1–3 We found it was very difficult for
the direct amination of 2 in the synthesis of
[18F]FDDNP, so we tried to activate the hydroxy
group of 2 for nucleophilic displacement by
transforming it into the tosylate 3 (Scheme 1).
Here, we reported its synthesis and the crystal
structure.
Synthesis of 1-(6-hydroxy-2-naphthyl)-
1-ethanone 2
A solution of 1.00 g of 1-(6-methoxy-2-
naphthyl)-1-ethanone in 2.5 mL of CH2Cl2 was
added to a mixture of 80 mL of HCl (d = 1.18)
and 15 drops (round 0.75 mL) of triethylamine in
a 100 mL three-neck round bottom flask equipped
with a reflux condenser and an isobaric dropping
(1) School of Chemical Engineering and the Environment, Beijing
Institute of Technology, Beijing 100081, P.R. China.
∗To whom correspondence should be addressed; e-mail: jiarongli@
hotmail.com.
789
ꢀ
C
1074-1542/05/1000-0789/0 2005 Springer Science+Business Media, Inc.

790
Jia-Rong and Guang
compound 3, melted at 119–120◦C. Anal. Calcd.
(%) for C19H16O4S: C, 67.04; H, 4.74; S, 9.42.
Found (%): C, 67.26; H, 4.87; S, 9.07; 1H NMR
(CD3COCD3, ppm): δ = 2.44 (s, 3H), 2.69 (s,
3H), 7.27 (dd, 1H), 7.46 (t, 2H,), 7.66 (d, 1H),
7.78 (d, 2H), 7.95 (d, 1H), 8.05 (dd, 1H), 8.10
(d, 1H), 8.64 (s, 1H). All sorption bands in IR
data of 3 appeared as expected. 1681 cm−1 corre-
Scheme 1.
−1
---
---
sponds to C O, 1594 cm corresponds to C C
--- ---
of naphthalene ring stretching absorption bands,
and 1369 cm−1 corresponds to O S O stretch-
--- ---
--- ---
ing absorption bands. The EI-MS of 3 gave the
molecular ion peaks (340, M) and those of the
main fragments.
funnel. The stirred mixture was heated quickly
to boil and reflux for 2 h. The hot solution was
filtered through a mineral wool plug to remove
the oily residue. The solid, after cooling, was
filtered out through a glass frit. Then the solid
was dissolved in 20 mL of ethyl acetate, washed
with brine, dried over with anhydrous magnesium
sulfate, and the solvent was removed under re-
duced pressure to give a crude product 2 0.74 g
(79.6%). The solid was dissolved in a base solu-
tion, and the diluted HCl was dropped in till white
deposit appeared entirely. The solid was filtered
out to afford pure product, melted at 172.5–174◦C
(Ref. 173.5–177◦C).4 All absorption bands in IR
data of 2 appeared as expected. 3365 cm−1 cor-
Table 1. Crystallographic Data and Structure Refinement for 3
Compound
CH3C6H4SO2OC10H6COCH3
CCDC deposit No.
253163
Chemical formula
Formula weight
Temperature (K)
Crystal size(mm)
Crystal system
C19H16O4S
340.38
293(2)
0.81 × 0.41 × 0.11
Orthorhombic
Pbca
Space group
Unit-cell dimensions
˚
a (A)
12.727(3)
14.560(3)
17.688(4)
3277.8(11)
8
---
responds to OH stretching absorption bands,
˚
b (A)
−1
1660 cm−1 corresponds to C O, and 1630 cm
---
---
˚
c (A)
---
3
corresponds to C C of naphthalene ring stretch-
˚
---
Volume (A )
Z
ing absorption bands. The EI-MS of 2 gave the
molecular ion peaks (186, M) and those of the
main fragments.
Color/shape
Colorless/platelet
1.379
0.217
Density (calcd.) (g/cm3)
Absorption coefficient (mm−1
F(000)
)
1424
Diffractometer/scan
Radiation/wavelength
ω
Synthesis of 2-acetylnaphthalen-6-yl
4-methylbenzosulfonate 3
Mo Kα (graphite
˚
monochrom.) 0.71073 A
2.30 ≤ θ ≤ 27.44
28209
θ range for data collection (◦)
Reflections collected
Independent/observed reflections 3733
Absorption correction
Max. and min. transmission
Refinement method
0.93 g (5 mmol) of 2, 1.00 g (5.24 mmol)
of p-toluenesulfonyl chloride, 10 drops (about
0.5 mL) of triethylamine, and 20 mL of tetrahy-
drofuran were added into a 50 mL three-neck
round bottom flask equipped with a reflux con-
denser. The resulted mixture was heated to re-
flux for 24 h. The solution was filtered out to
remove the indissoluble substance and the filtrate
was evaporated to give 1.23 g (72%) of 3. Re-
crystallization from ethyl acetate to give the title
Empirical
0.9759 and 0.8438
Full-matrix least-squares
on F2
3733/0/217
0.846
R1 = 0.0402, wR2 = 0.0600
R1 = 0.1097, wR2 = 0.0660
0.208, −0.229
Data/restraints/parameters
Goodness of fit on F2
Final R indices [I ≥ 2σ(I)]
R indices (all data)
Largest diff. Peak and
−3
˚
hole (e A
)

Synthesis and crystal structure
791
Fig. 1. Molecular structure of 3. Thermal ellipsoids are at the 50% probability level.
X-ray crystallography
In the molecular structure of 3, acetyl group
is a planar with naphthalene ring, and the dihedral
angle between the benzene ring and the naphtha-
lene ring is 116.5◦.
There are no hydrogen bonds in the crys-
tal of 3. But three types of short contacts which
belong to van der Waals force exist and the
crystal of 3 is formed through them. The bond
lengths and bond angles of three types of short
contacts are listed in Table 3. Three types of
short contacts in the crystal of 3 are shown in
Fig. 3.
The colorless single crystal was cultured
from a solution of ethyl acetate by slow evapo-
ration at room temperature.
A single crystal of approximate dimensions
0.81 mm × 0.41 mm × 0.11 mm was used. X-
ray diffraction data were collected at 293(2) K
on a Rigaku Raxis Rapid IP diffractometer, us-
ing graphite monochromatized Mo Kα radia-
˚
tion (λ = 0.71073 A). A total of 1424 indepen-
dent reflections were collected in the range of
2.30◦ ≤ θ ≤ 27.44◦ by ω scan mode. The crystal
data, data collection, and refinement parameters
for 3 were presented in Table 1.
---
The C C bond lengths and angles of the
naphthalene ring in 3 are in the same range as
those found in the relative compounds, such as
3-hydroxy-2-naphthalenecarboxaldehyde.7 The
The structure was solved by direct meth-
ods using the program SHELXS-97.5 Refine-
ments were done by the full-matrix least-squares
on F2 using SHELXL-97.6 Nonhydrogen atoms
were refined with anisotropic displacement pa-
rameters. All hydrogen atoms were located from
a difference Fourier map and refined without
restraints.
˚
---
length (1.417 A) of single C O bond of prod-
---
uct 3 is longer than that of single C O bond
Results and discussion
The molecular structure of the compound
3 is illustrated in Fig. 1. The molecular pack-
ing of the title compound 3 is shown in Fig. 2.
The bond lengths and bond angles are listed in
Table 2.
Fig. 2. The packing diagram of 3.

792
Jia-Rong and Guang
◦
˚
Table 2. Bond Lengths (A) and Angles ( ) for 3
Angles (◦)
Bonds
Lengths (A)
˚
Bonds
----
----
----
----
----
O(2) S(1) O(1)
120.75(10)
109.11(8)
102.12(9)
109.50(10)
109.37(10)
104.65(8)
117.8(2)
122.0(2)
120.3(2)
122.0(2)
119.3(2)
S(1) O(2)
----
S(1) O(1)
1.4217(15)
1.4292(14)
1.5983(13)
1.751(2)
1.507(3)
1.368(3)
1.383(3)
1.379(3)
1.378(3)
1.369(3)
1.378(3)
1.348(2)
1.397(2)
1.417(2)
1.361(2)
1.411(2)
1.409(2)
1.419(2)
1.414(3)
1.421(2)
1.356(2)
1.414(2)
1.363(2)
1.496(3)
1.209(2)
1.502(3)
O(2) S(1) O(3)
---- ----
----
O(1) S(1) O(3)
---- ----
S(1) O(3)
----
O(2) S(1) C(5)
---- ----
S(1) C(5)
----
O(1) S(1) C(5)
---- ----
C(1) C(2)
----
O(3) S(1) C(5)
---- ----
C(2) C(3)
----
C(3) C(2) C(7)
---- ----
C(2) C(7)
----
C(3) C(4)
C(3) C(2) C(1)
---- ----
----
C(7) C(2) C(1)
---- ----
C(4) C(5)
----
C(2) C(3) C(4)
---- ----
C(5) C(6)
----
C(6) C(7)
C(5) C(4) C(3)
---- ----
----
C(6) C(5) C(4)
---- ----
119.7(2)
C(8) C(13)
----
C(8) C(9)
C(6) C(5) S(1)
---- ----
119.93(17)
120.26(17)
120.1(2)
----
C(4) C(5) S(1)
---- ----
C(8) O(3)
----
C(9) C(10)
C(5) C(6) C(7)
---- ----
----
C(6) C(7) C(2)
---- ----
121.1(2)
C(10) C(11)
----
C(11) C(17)
C(13) C(8) C(9)
---- ----
122.82(18)
120.23(18)
116.75(18)
119.08(18)
120.92(18)
122.02(18)
118.93(17)
119.03(18)
118.34(18)
122.76(19)
118.88(18)
119.23(18)
120.95(19)
121.22(19)
118.67(19)
122.67(18)
118.63(18)
121.87(18)
119.9(2)
----
C(13) C(8) O(3)
---- ----
C(11) C(12)
----
C(12) C(14)
C(9) C(8) O(3)
---- ----
----
C(10) C(9) C(8)
---- ----
C(12) C(13)
----
C(14) C(15)
C(9) C(10) C(11)
---- ----
----
C(17) C(11) C(10)
---- ----
C(15) C(16)
----
C(16) C(17)
C(17) C(11) C(12)
---- ----
----
C(10) C(11) C(12)
---- ----
C(16) C(18)
----
C(18) O(4)
C(14) C(12) C(11)
---- ----
----
C(14) C(12) C(13)
---- ----
C(18) C(19)
C(11) C(12) C(13)
---- ----
C(8) C(13) C(12)
---- ----
C(15) C(14) C(12)
---- ----
C(14) C(15) C(16)
---- ----
C(17) C(16) C(15)
---- ----
C(17) C(16) C(18)
---- ----
C(15) C(16) C(18)
---- ----
C(16) C(17) C(11)
---- ----
O(4) C(18) C(16)
---- ----
O(4) C(18) C(19)
---- ----
120.6(2)
119.47(19)
120.76(12)
C(16) C(18) C(19)
---- ----
C(8) O(3) S(1)
in the relative compounds, such as 2-hydroxy-
7
˚
1-naphthalenecarboxaldehyde (1.358 A). This
---
demonstrates the single C O bond of 3 is
Table 3. The Short Contact in the Crystal of 3
Bounds
Numbers
Lengths (A) Angles (◦)
˚
---
---
---
C
C
C
H· · · π
H· · ·O
H· · · π
2
2
2
2.892
2.496
2.871
145.97
157.12
135.46
Fig. 3. Three types of short contacts in crystal of 3.

Synthesis and crystal structure
793
easily ruptured and the amination is easily carried
out.
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Supplementary material CCDC-253163 contains the supplemen-
tary crystallographic data for this paper. These data can be obtained
free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html or from
the Cambridge Crystallographic Data Centre (CCDC), 12 Union
Road, Cambridge CB2 1EZ, United Kingdom; Direct Line: +44
1223 762910. Tel: +44 1223 336408. Fax: +44 1223 336033;
E-mail: linstead@ccdc.cam.ac.uk; deposit@ccdc.cam.ac.uk.
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Acknowledgment
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This work was supported by the grant of
Beijing Institute of Technology.