Synthesis and structures of 9-triptycylallene derivatives

Article abstract of DOI:10.1246/bcsj.79.1293

9-Triptycylallene (1) was synthesized by LiAlH₄ reduction of 1-(9-triptycyl)-2-propynyl methanesulfonate (7), and three 3-substituted derivatives of 1 were also obtained by reacting compound 7 with appropriate metal reagents. LiAlH₄

Full text of DOI:10.1246/bcsj.79.1293

Ó 2006 The Chemical Society of Japan
Bull. Chem. Soc. Jpn. Vol. 79, No. 8, 1293–1299 (2006) 1293
Synthesis and Structures of 9-Triptycylallene Derivatives
ꢀ
Mao Minoura, and Yasuhiro Mazaki
Gaku Yamamoto, Yuriko Kobayashi, Kasumi Ono, Emiko Yano,
Department of Chemistry, School of Science, Kitasato University, 1-15-1 Kitasato, Sagamihara 228-8555
Received March 13, 2006; E-mail: gyama@kitasato-u.ac.jp
9-Triptycylallene (1) was synthesized by LiAlH4 reduction of 1-(9-triptycyl)-2-propynyl methanesulfonate (7), and
three 3-substituted derivatives of 1 were also obtained by reacting compound 7 with appropriate metal reagents. LiAlH4
reduction of 1,3-di(9-triptycyl)-2-propynyl methanesulfonate (10) gave 1,3-di(9-triptycyl)propyne (12). The molecular
structures of some of the allenes and of the propyne were determined by X-ray crystallography. As well, the allenes
and some of the related compounds were characterized by NMR spectroscopy.
1
Unique stereochemical features of an allene moiety have
been of interest for quite some time, and a vast amount of
research has been reported on the synthesis, structures, and
reported, and it has been shown that treatments of LiAlH4
and various organocuprate reagents with 2-propynyl sulfonates
0
4
afford allenes by SN2 -type reactions. Therefore, 1-(9-tripty-
cyl)-2-propynyl methanesulfonate (7) was used as the precur-
sor for the target compounds 1–4, and the synthetic route is
shown in Scheme 1.
1
chiroptical properties of allene derivatives. During the course
of our studies on the static and dynamic stereochemistry of
2
triptycene derivatives, we have been interested in the stereo-
5
chemical behavior of 9-triptycylallene derivatives. In this arti-
cle, we report and discuss the synthesis of 9-triptycylallene (1)
and several 3-substituted derivatives: 3-methyl (2), 3-phenyl
It had been reported that triptycene-9-carbaldehyde (5) can
not be obtained directly from the reaction of anthracene-9-car-
baldehyde with benzyne generated by thermal decomposition
of benzenediazonium-2-carboxylate and that the formyl group
should be protected in advance, e.g., as an acetal. However, we
found that the direct reaction of anthracene-9-carbaldehyde
with benzyne gave compound 5 in a moderate yield (47%).
The reaction of compound 5 with ethynylmagnesium bro-
mide afforded 1-(9-triptycyl)-2-propyn-1-ol (6), which was
then converted to the methanesulfonate 7. Compound 1 was
obtained by LiAlH4 reduction of the methanesulfonate 7. Re-
actions of compound 7 with the cuprate reagents, prepared by
reacting commercially available methyllithium and phenyl-
lithium with copper(I) iodide, gave the allenes 2 and 3, respec-
tively, in moderate yields. The 9-triptycyl cuprate reagent
could only be prepared when CuI was dried thoroughly under
(
3), and 3-(9-triptycyl) (4). In addition, X-ray crystallography
of compounds 1, 3, and 4, and the NMR spectroscopy of com-
pounds 1–4 are reported (Chart 1).
Compound 4 is an extended analog of bis(9-triptycyl)-X
compounds (Tp2X), which have been extensively studied by
Iwamura’s and Mislow’s groups because they behave like
3
tightly meshed molecular bevel gears.
Results and Discussion
Synthesis. Various synthetic routes to allenes have been
R
H
C
ꢁ
high vacuum at ca. 100 C for 10 h. Compound 4 was produced
in 98% yield.
H
C
C
1: R = H
2
3
4
: R = CH3
As for the synthesis of 1,3-di(9-triptycyl)allene (4), we at
first attempted the routes shown in Scheme 2 with the expecta-
tion that LiAlH4 reduction of a 1,3-di(9-triptycyl)-2-propynyl
derivative, i.e., compounds 8, 9, or 10, would afford compound
4. Reaction of triptycene-9-carbaldehyde (5) with 9-triptycyl-
: R = C H5
6
: R = 9-Triptycyl (Tp)
Chart 1.
HC CMgBr
OH
CH SO Cl
OSO CH3
2
3
2
Tp CHO
Tp CH C CH
Tp CH C CH
5
6
7
Tp = 9-triptycyl
LiAlH4
"
R CuLi"
2
Tp CH
C
CH2
Tp CH
C
CH R
1
2−4
Scheme 1.
Published on the web August 7, 2006; doi:10.1246/bcsj.79.1293

1
294 Bull. Chem. Soc. Jpn. Vol. 79, No. 8 (2006)
9-Triptycylallenes
˚
ethynyllithium gave the alcohol 8, which was then converted
to the acetate 9 and the methanesulfonate 10. The reaction
of compound 8 with LiAlH4 did not proceed at all, and the
treatment of the acetate 9 with LiAlH4 resulted in the forma-
tion of what was speculated to be (E)-1,3-di(9-triptycyl)-2-
which is somewhat longer, 1.318 A, presumably because of
conjugation with the phenyl group. The Tp–C bond lengths
˚
lie in a narrow range of 1.505–1.512 A, while the Ph–C bond
˚
length in compound 3 is 1.471 A. The difference in lengths is
2
3
2
2
ascribed to sp –sp and sp –sp bond characters. The Tp–C=C
ꢁ
1
propen-1-ol (11) by H NMR spectral data. Reaction of com-
bond angles are 126–132 and are significantly larger than the
2
ꢁ
pound 10 with LiAlH4 gave 1,3-di(9-triptycyl)propyne (12)
as the sole product via an SN2-type displacement of the sulfo-
nate group.
typical sp bond angle of 120 . The C=C=C moiety is almost
linear in compounds 1 and 3, while slightly bent in compound
4, due to the steric repulsion between the two Tp groups. The
Tp–C and Ph–C bonds in compound 3 and the two Tp–C bonds
X-ray Crystallography. The molecular structures of the
allenes 1, 3, and 4, and of the propyne 12 were determined
by X-ray crystallography. Single crystals suitable for the anal-
ysis were obtained by recrystallization from diethyl ether–
methanol for 1 and 3, and from ethyl acetate–hexane for 4.
Crystals of compound 4 contained ethyl acetate molecules in
a 1:1 ratio: The molecular structure of 4 could be definitely
determined, while that of ethyl acetate could not be refined,
because the molecule seemed to turn around within a cavity
formed by molecules of 4. Crystallization of compound 12
from chloroform afforded crystals containing one chloroform
molecule per one molecule of 12. ORTEP drawings of com-
pounds 1 and 3 are shown in Fig. 1, and those of compounds
ꢁ
in compound 4 have dihedral angles of 96.4 and 102.9 , re-
spectively, that are considerably larger than the orthogonality.
The large angles are also ascribed to the steric repulsion be-
tween the terminal groups.
In compounds 1 and 3, the allene moiety does not bisect the
dihedral angle between the planes of the two flanking benzene
ꢁ
rings in the Tp group, but is twisted by ca. 15 to avoid eclips-
ing the allenic hydrogen with the peri-hydrogen of the third
benzene ring (Fig. 1 and Table 1). One of the Tp groups in
compound 4—the one bonded to C1 in Fig. 2—adopts ar-
rangement similar to those in compounds 1 and 3, while the
other Tp group, bonded to C3 in Fig. 2, is twisted differently
4
and 12 are shown in Figs. 2 and 3, respectively. Selected
(
a)
bond lengths and angles of the allenes are listed in Table 1,
and those of 12 are listed in Table 2.
The lengths of the C=C bonds of the allene moieties are
3
2
1
7
˚
2
3
1
.287–1.300 A, except for the C =C bond in compound 3,
4
5
1
5
2
3
TpC CLi
OH
6
Tp CHO
Tp CH C C Tp
5
8
Ac O
2
CH SO Cl
(b)
3
2
OCOCH3
OSO CH
2 3
1
3
9
Tp CH C C Tp
Tp CH C C Tp
2
6
8
5
1
4
9
10
5
3
2
LiAlH4
LiAlH4
7
Tp CH CH CH Tp Tp CH2 C C Tp
OH
11
12
Fig. 1. ORTEP diagrams with 50% probability ellipsoids of
(a) compound 1, and (b) compound 3.
Scheme 2.
(a)
(b)
(c)
4
5
8
'
2
3
8
1
6
3
2
6
'
2
1
4
6
'
7
6
7
7'
1
3
5
5'
Fig. 2. ORTEP diagrams of compound 4 with 50% probability ellipsoids; (a) the side view, (b) looking down along the C1–C4
bond, and (c) looking down along the C3–C8 bond.

G. Yamamoto et al.
Bull. Chem. Soc. Jpn. Vol. 79, No. 8 (2006) 1295
Table 3. 1H and 13C NMR Data of the Allene Moieties of
aÞ
Compounds 1–4
11
H 1'
C C C
Tp
2' 3'
R
H
1
0
3
2
8
9
1
4
5
6
1
H
2
3
4
7
R =
CH3
C6H5
Tp
0
0
1
3
1
-H
-H
-C
6.474
6.402
(dq, 7.2, 3.6)
5.547
(quint, 7.2)
85.47
208.50
6.896
(d, 6.9)
6.667
(d, 6.9)
91.20
7.016
(s)
7.016
(s)
90.14
209.43
90.14
(
t, 7.1)
5.193
d, 7.1)
85.61
Fig. 3. ORTEP diagram of compound 12 with 50% prob-
ability ellipsoids.
(
0
0
˚
Table 1. Selected Bond Lengths (A) and Angles ( )
ꢁ aÞ
2 -C
211.65
78.09
207.69
97.25
0
3
-C
88.39
1
3
4
a) In parentheses are multiplicities and coupling constants in
Hz.
1
2
1
3
4
4
4
–2
–3
–4
–8
–5
–6
–7
1.287(2)
1.295(2)
1.510(2)
—
1.547(2)
1.545(2)
1.547(2)
1.289(3)
1.318(4)
1.505(3)
1.471(4)
1.547(3)
1.553(3)
1.542(3)
1.299(3)
1.300(3)
1.512(3)
1.508(2)
In the propyne 12, the two CꢂC–C angles are 170.9 and
ꢁ
1
75.3 and the triple bond moiety is slightly bent so that the
bÞ
bÞ
bÞ
1.536(3), 1.542(2)
1.540(3), 1.550(2)
1.543(3), 1.539(2)
two Tp groups are closer to each other: Attractive van der
Waals forces may occur between the two Tp moieties. The
Tp–CH2 bond is almost staggered, while the C1–C4 and C8–
C9 bonds are nearly eclipsed with a dihedral angle of ca.
1
2
2
1
1
1
–2–3
–3–8
–1–4
–4–5
–4–6
–4–7
177.8(2)
—
128.4(2)
113.1(2)
113.5(2)
115.7(2)
179.0(3)
125.7(3)
125.8(2)
114.7(2)
111.1(2)
116.6(2)
172.6(2)
131.5(2)
126.2(2)
ꢁ
10 (Fig. 3 and Table 2).
NMR Spectra. 1H and 13C NMR data of the allene moie-
ties of compounds 1–4 are compiled in Table 3. Assignments
of the proton chemical shifts, if not obvious, were made by use
of NOE experiments. In compound 3, irradiation of the signal
at ꢀ 7.71, assignable to the peri-protons (1-, 8-, and 13-H) of
the Tp moiety, enhanced the doublet signal at ꢀ 6.90, which
bÞ
bÞ
bÞ
114.2(2), 111.3(2)
110.2(2), 118.1(2)
116.7(2), 112.5(2)
4
2
2
2
2
–1–3–8
–1–4–5
–1–4–6
–1–4–7
–3–8–9
—
96.4
ꢄ163.6(3)
77.4(3)
102.9
bÞ
bÞ
bÞ
ꢄ168.7
ꢄ165.8(2), 144.3(2)
77.1(3), 23.4(2)
ꢄ43.3(3), ꢄ98.5(2)
0
was, therefore, assigned to 1 -H. The large coupling constants
4
72.2
ꢄ48.0
—
5
ꢄ42.6(4)
across the allene moiety ( J ꢃ 7 Hz and J ꢃ 4 Hz) have been
reported for other compounds.6
ꢄ170.0(3)
The carbon chemical shifts were assigned by CH-COSY ex-
periments, when ambiguous. It has been well documented that
a) The numbering is shown in Figs. 1 and 2. b) The atom num-
0
0
0
bers 1, 4, 5, 6, and 7 should be read as 3, 8, 5 , 6 , and 7 ,
respectively.
2
the sp carbons of alkyl- or aryl-substituted allenes appear at a
significantly high field (ꢀ 80–100) and the sp carbon appears at
7
˚
Table 2. Selected Bond Lengths (A) and Angles ( ) of
ꢁ
a very low field (ꢀ 200–210).
aÞ
Stereodynamics. In any of the allenes 1–4, the three ben-
zene rings of the Tp moiety are equivalent in the NMR spectra
at room temperature, indicating that rotation around the Tp–C
bond is very fast on the NMR timescale. This is not surprising
Compound 12
1–2
2–3
3–8
1–4
4–5
4–6
4–7
8–9
8
8
1.478(4) 1–2–3
1.186(4) 2–3–8
1.466(4) 2–1–4
1.540(4) 1–4–5
1.536(4) 1–4–6
1.544(4) 1–4–7
1.535(4) 3–8–9
175.3(3) 2–1–4–5
170.9(3) 2–1–4–6
112.7(2) 2–1–4–7
112.7(2) 4–1–8–9
177.3
58.3
ꢄ65:5
10.4
3
2
because rotation about a C(sp )–C(sp ) bond has a low energy
barrier except in special cases.8
Compound 4 showed a single sharp ABCD-pattern spectrum
113.9(2) 4–1–8–10 ꢄ104:0
114.3(2) 4–1–8–11
112.2(2)
133.4
ꢁ
for the aromatic protons in CD2Cl2 at ꢄ107 C. This shows
that the rotations of the Tp–C bonds are fast even at this low
temperature, although it is not yet clear whether rotation of
the two Tp–C bonds take place independently or in a correlat-
1.532(4) 3–8–10 115.9(2)
–10 1.541(4) 3–8–11 112.9(2)
–11 1.540(4)
ed fashion as dynamic molecular bevel gears.
1H NMR spectra of the propynyl compounds 6, 7, 8, 9, and
0 at room temperature showed that the three benzene rings of
a) The numbering is shown in Fig. 3.
1
the 1-Tp group are not equivalent because of slow rotation
(
Fig. 2 and Table 1). Therefore, the torsion angles between the
3
Tp and allene moieties are determined not only by the steric
repulsions between the Tp and allene moieties but also by
the repulsion between the two Tp moieties. The two Tp skel-
etons in compound 4 are well meshed with each other, like
bevel gears.
around the Tp–C(sp ) bond on the NMR timescale, while the
benzene rings of the 3-Tp group in compounds 8–10 are equiv-
alent reflecting fast rotation about the Tp–C(sp) bond. For ex-
ample, the peri-proton (1-, 8-, and 13-H) signals of 1-Tp group
of 6 in toluene-d8 appeared as three sharp doublets at the low-

1
296 Bull. Chem. Soc. Jpn. Vol. 79, No. 8 (2006)
9-Triptycylallenes
butanone was slowly added a slurry of benzenediazonium-2-car-
boxylate,12 prepared from 5.49 g (40.0 mmol) of anthranilic acid,
in 60 mL of butanone over the course of 50 min, and the mixture
was heated under reflux for another 30 min. After evaporation of
the solvent, the residue was subjected to column chromatography
through silica gel with dichloromethane–hexane (1:1) as the elu-
ent. Recrystallization of the eluate from dichloromethane–hexane
CH3
H
CH3
R
H
H
C
C
Cl
Cl
1
3
14a: R = C H5
4b: R = Cl
ꢁ
6
gave 1.33 g (4.71 mmol, 47%) of compound 5, mp 243–247 C
1
5
ꢁ
1
(
(
(
lit. 235–238 C). H NMR (CDCl3) ꢀ 5.401 (1H, s), 7.01–7.08
6H, m), 7.429 (3H, m), 7.619 (3H, m), 11.217 (1H, s). C NMR
13
Chart 2.
CDCl3) ꢀ 54.15 (1C, t), 60.83 (1C, q), 122.41 (3C, t), 124.06 (3C,
t), 125.19 (3C, t), 125.81 (3C, t), 142.59 (3C, q), 145.78 (3C, q),
est field of the aromatic region. The signals broadened upon
elevation of the temperature, but did not coalesce even at 117
2
00.98 (1C, t).
-(9-Triptycyl)-2-propyn-1-ol (6). To an ice-cold solution of
.00 g (10.6 mmol) of triptycene-9-carbaldehyde (5) in 30 mL of
1
ꢁ
ꢄ1
C. Lineshape analysis afforded a rate constant k of 20 s at
ꢁ
3
z
1
of 86.7 kJ mol at this temperature. This is comparable with
17 C, with a corresponding free energy of activation, ꢀG ,
ꢄ1
anhydrous tetrahydrofuran (THF) was added 50.8 mL (25.4 mmol)
of a 0.5 M solution of ethynylmagnesium bromide in THF, and the
mixture was stirred for 2 h, during which time the temperature was
allowed to increase to room temperature. The reaction mixture
was quenched with water and extracted with diethyl ether. The ex-
tracts were washed with brine, dried over MgSO4, and evaporated.
Column chromatography of the residue through silica gel with
hexane–dichloromethane (5:1) as the eluent gave 2.69 g (8.72
z
ꢄ1
ꢁ
i
ꢀ
bond in 2,3-dichloro-9-isopropyltriptycene (13), a prototype
G ¼ 86:2 kJ mol at 100 C for the rotation of the Tp– Pr
of triptycene derivatives carrying a secondary alkyl group at
9
the bridgehead (Chart 2).
1
In the H NMR spectrum of the propyne 12, the peri-protons
1-, 8-, and 13-H) of the Tp group bonded to the methylene
(
ꢁ
carbon had a very broad single peak at room temperature,
which split into two signals with the intensity ratio of 2:1 upon
lowering the temperature, indicating the slow-down of the
Tp–CH2 bond rotation. Lineshape analysis at four tempera-
mmol, 82%) of compound 6, mp 257–259 C (dec). Found: C,
89.64; H, 5.25%. Calcd for C23H16O: C, 89.58; H, 5.23%.
1
H NMR (CDCl3) ꢀ 2.696 (1H, d, J ¼ 4:6 Hz, OH), 2.807 (1H, d,
J ¼ 2:3 Hz, CCH), 5.351 (1H, s), 6.125 (1H, dd, J ¼ 4:6, 2.3 Hz),
ꢁ
6
.93–7.12 (6H, m), 7.32–7.38 (2H, m), 7.44 (1H, m), 7.63–7.71
tures in the range of ꢄ28 to 21 C gave the following kinetic
13
z
ꢄ1
z
(2H, m), 8.18 (1H, m). C NMR (CDCl ) ꢀ 54.50 (1C, t), 58.08
parameters: ꢀH ¼ 49:4 ꢅ 0:3 kJ mol , ꢀS ¼ ꢄ15:9 ꢅ 1:4
3
ꢄ1 ꢄ1
z
ꢁ
ꢄ1
(1C, q), 62.02 (1C, t), 77.80 (1C, t), 83.13 (1C, q), 122.72 (1C,
J mol
z
K
, ꢀG (0 C) = 53.7 kJ mol . For comparison,
ꢀG (0 C) for 9-benzyltriptycene (14a) and 9-chloromethyl-
1
triptycene (14b), which have a primary alkyl group at the
bridgehead, are 45.8 and 58.5 kJ mol , respectively, for the
Tp–CH2 bond rotation (Chart 2). The barrier height for com-
pound 12 lies between those for compounds 14a and 14b.
ꢁ
10
t), 123.02 (1C, t), 123.39 (1C, t), 123.50 (1C, t), 123.84 (1C, t),
124.59 (1C, t), 124.65 (1C, t), 124.68 (1C, t), 125.00 (1C, t),
125.19 (1C, t), 125.21 (1C, t), 125.46 (1C, t), 141.07 (1C, q),
1
ꢄ1
1
1
43.77 (1C, q), 144.01 (1C, q), 146.15 (1C, q), 147.02 (1C, q),
47.04 (1C, q).
1
-(9-Triptycyl)-2-propynyl Methanesulfonate (7).
To an
ice-cold solution of 1.54 g (5.00 mmol) of compound 6 in 50 mL
of anhydrous THF was added 4.50 mL (7.0 mmol) of a 1.54 M
solution of butyllithium in hexane, and the mixture was stirred
for 1 h at 0 C. To this solution was added 0.54 mL (7.0 mmol)
of methanesulfonyl chloride, and the mixture was stirred for
Conclusion
Four 9-triptycylallenes have been synthesized and charac-
terized. Especially, 1,3-di(9-triptycyl)allene (4) was shown to
be static molecular bevel gears. We are trying to determine
whether 4 behaves as dynamic molecular gears. In order to
do this, we are synthesizing a derivative with labels on the
Tp moieties and studying whether it shows phase isomerism.3
Since compounds 1–4 are chiral, resolution and chiroptical
studies of these compounds are also underway.
ꢁ
2
4 h at room temperature. The mixture was poured onto ice-water
and extracted with diethyl ether. The extracts were washed with
brine, dried over MgSO4, and evaporated. Column chromatogra-
phy of the residue through silica gel with dichloromethane as
the eluent followed by recrystallization from dichloromethane–
hexane gave 0.516 g (1.34 mmol, 27%) of compound 7, mp 132–
ꢁ
Experimental
1
34 C. Found: C, 74.58; H, 4.78%. Calcd for C24H18O3S: C,
General. Melting points are not corrected. H and 13C NMR
1
74.59; H, 4.69%. H NMR (CDCl3) ꢀ 3.057 (1H, d, J ¼ 2:3 Hz),
3.419 (3H, s), 5.360 (1H, s), 6.854 (1H, d, J ¼ 2:3 Hz), 6.96–
7.12 (6H, m), 7.34–7.40 (2H, m), 7.45 (1H, m), 7.54 (1H, m), 7.61
1
spectra were obtained on a Bruker ARX-300 spectrometer oper-
1
13
ating at 300.1 MHz for H and 75.4 MHz for C, respectively.
Chemical shifts are referenced to internal tetramethylsilane (ꢀ
.00) and CDCl3 (ꢀC 77.00). The letters p, s, t, and q written beside
13
H
(1H, m), 8.00 (1H, m). C NMR (CDCl3) ꢀ 40.42 (1C, p), 54.41
(1C, t), 57.15 (1C, q), 69.64 (1C, t), 78.32 (1C, q), 81.80 (1C, t),
121.94 (1C, t), 122.51 (1C, t), 123.64 (1C, t), 123.66 (1C, t),
123.72 (1C, t), 124.58 (1C, t), 124.68 (1C, t), 124.78 (1C, t),
125.28 (1C, t), 125.43 (1C, t), 125.55 (1C, t), 125.78 (1C, t),
140.39 (1C, q), 142.48 (1C, q), 142.73 (1C, q), 145.37 (1C, q),
146.53 (1C, q), 146.81 (1C, q).
0
13
the C chemical shifts denote primary, secondary, tertiary, and
quaternary, respectively. In the variable-temperature experiments,
temperatures were calibrated using a methanol or an ethylene gly-
ꢁ
col sample and are reliable to ꢅ1 C. Preparative gel permeation
chromatography (GPC) was performed on an LC-908 Liquid
Chromatograph (Japan Analytical Industry Co., Ltd.) using a series
of JAIGEL 1H and 2H columns and chloroform as the eluent.
1-(9-Triptycyl)propadiene (1).
To a solution of 100 mg
(0.26 mmol) of compound 7 in 10 mL of anhydrous THF was
added 30 mg (0.78 mmol) of LiAlH4 and the mixture was heated
under reflux for 24 h. The reaction mixture was treated with aq
Triptycene-9-carbaldehyde (5). To a boiling solution of
.06 g (10.0 mmol) of anthracene-9-carbaldehyde in 60 mL of
2

G. Yamamoto et al.
Bull. Chem. Soc. Jpn. Vol. 79, No. 8 (2006) 1297
NH4Cl and extracted with diethyl ether. The ether layer was wash-
ed with water and dried over MgSO4, and the solvent was evapo-
rated. Recrystallization of the residue from dichloromethane–
hexane afforded 48 mg (0.164 mmol, 63%) of 1, mp 201–202 C.
Found: C, 94.25; H, 5.56%. Calcd for C23H16: C, 94.48; H, 5.52%.
(1:1) as the eluent gave 207 mg (0.380 mmol, 98%) of compound
ꢁ
4, mp 311–312 C (from diethyl ether–methanol). Found: C,
1
94.85; H, 5.22%. Calcd for C43H28: C, 94.82; H, 5.18%. H NMR
ꢁ
(CDCl3) ꢀ 5.441 (2H, s, 10-H), 6.878 (6H, td, J ¼ 7:5, 1.2 Hz,
2/7/14-H), 6.996 (6H, td, J ¼ 7:5, 1.2 Hz, 3/6/15-H), 7.016 (2H,
s), 7.418 (6H, dd, J ¼ 7:2, 1.2 Hz, 4/5/16-H), 7.815 (6H, d, J ¼
1
0
H NMR (CDCl3) ꢀ 5.193 (2H, d, J ¼ 7:1 Hz, 3 -H), 5.382 (1H, s,
0
13
1
0-H), 6.474 (1H, t, J ¼ 7:1 Hz, 1 -H), 7.03–7.13 (6H, m), 7.373
7:5 Hz, 1/8/13-H). C NMR (CDCl3) ꢀ 53.73 (2C, q), 54.22 (2C,
1
3
(
3H, m), 7.618 (3H, m). C NMR (CDCl3) ꢀ 53.29 (1C, q), 54.16
t), 90.14 (2C, t), 122.70 (6C, t), 123.53 (6C, t), 124.89 (6C, t),
125.27 (6C, t), 145.62 (6C, q), 145.84 (6C, q), 209.43 (1C, q).
1,3-Di(9-triptycyl)-2-propyn-1-ol (8). To a solution of 1.17 g
(4.20 mmol) of 9-ethynyltriptycene13 in 10 mL of dry diethyl ether
(
1
1C, t), 78.09 (1C, s), 85.61 (1C, t), 122.23 (3C, t), 123.53 (3C, t),
24.78 (3C, t), 125.23 (3C, t), 145.79 (6C, q), 211.65 (1C, q).
1
-(9-Triptycyl)-1,2-butadiene (2). To a suspension of 380 mg
ꢁ
ꢁ
(
2.0 mmol) of copper(I) iodide in 30 mL of diethyl ether at ꢄ20 C
was added at 0 C under argon 2.5 mL (4.00 mmol) of 1.59 M
was added 3.50 mL (4.0 mmol) of a 1.14 M solution of methyl-
lithium in diethyl ether, and the mixture was stirred for 0.5 h at
this temperature. To this mixture was added 230 mg (0.59 mmol)
of the methanesulfonate 7, and the mixture was stirred for 2 h. The
mixture was poured into water, and the organic layer was washed
with aq NH4Cl and dried over MgSO4. Column chromatography
through silica gel with dichloromethane as the eluent followed
by preparative GPC afforded 90.0 mg (0.29 mmol, 49%) of com-
butyllithium in hexane and the solution was stirred for 30 min at
room temperature. To the solution was added 1.20 g (4.25 mmol)
of 5 in 10 mL of diethyl ether, and the mixture was stirred for 3 h.
The mixture was quenched with ice-water and extracted with
diethyl ether. The ether layer was washed with brine and dried
over MgSO4, and the ether was then evaporated. Column chroma-
tography through silica gel with hexane–ethyl acetate (2:1) as the
eluent afforded 1.83 g (3.26 mmol, 77%) of compound 8, mp 302–
ꢁ
ꢁ
pound 2, mp 122–123 C (from dichloromethane–hexane). Found:
C, 93.87; H, 6.01%. Calcd for C24H18: C, 94.08; H, 5.92%.
304 C (dec). Found: C, 92.29; H, 5.04%. Calcd for C43H28O: C,
1
92.11; H, 5.03%. H NMR (CDCl3) ꢀ 3.023 (1H, d, J ¼ 4:8 Hz,
1
H NMR (CDCl3) ꢀ 1.913 (3H, dd, J ¼ 7:2, 3.6 Hz, CH3), 5.384
OH), 5.381 (1H, s), 5.443 (1H, s), 6.685 (1H, d, J ¼ 4:8 Hz),
6.89–7.13 (12H, m), 7.350 (3H, dd, J ¼ 7:2, 1.2 Hz), 7.423 (2H,
m), 7.504 (1H, m), 7.652 (3H, dd, J ¼ 7:1, 1.2 Hz), 7.866 (1H, d,
0
(
1H, s, 10-H), 5.547 (1H, quint, J ¼ 7:2 Hz, 3 -H), 6.402 (1H, dq,
0
J ¼ 7:2, 3.6 Hz, 1 -H), 6.95–7.05 (6H, m), 7.37 (3H, m), 7.61 (3H,
13
13
m). C NMR (CDCl3) ꢀ 14.20 (1C, p), 53.76 (1C, q), 54.22 (1C,
t), 85.47 (1C, t), 88.39 (1C, t), 122.29 (3C, t), 123.49 (3C, t),
J ¼ 7:1 Hz), 8.053 (1H, m), 8.581 (1H, m). C NMR (CDCl3) ꢀ
53.23 (1C, t), 53.33 (1C, q), 54.60 (1C, t), 58.51 (1C, q), 62.91
(1C, t), 84.35 (1C, q), 92.12 (1C, q), 122.62 (3C, t), 123.09 (1C, t),
123.16 (1C, t), 123.39 (3C, t), 123.52 (1C, t), 123.63 (1C, t),
123.96 (1C, t), 124.60 (1C, t), 124.68 (1C, t), 125.09 (3C, t),
125.10 (1C, t), 125.15 (1C, t), 125.27 (1C, t), 125.32 (1C, t),
125.59 (1C, t), 125.66 (3C, t), 141.20 (1C, q), 143.97 (1C, q),
144.22 (3C, q), 144.27 (3C, q), 144.32 (1C, q), 146.29 (1C, q),
147.19 (1C, q), 147.32 (1C, q).
1
2
24.75 (3C, t), 125.15 (3C, t), 145.90 (3C, q), 146.01 (3C, q),
08.50 (1C, q).
1-Phenyl-3-(9-triptycyl)propadiene (3). To a suspension of
00 mg (2.60 mmol) of copper(I) iodide in 30 mL of diethyl ether
at ꢄ20 C was added 5.00 mL (5.20 mmol) of a 1.04 M solution of
phenyllithium in cyclohexane–diethyl ether, and the mixture was
stirred for 1 h at this temperature. To this mixture was added
5
ꢁ
2
50 mg (0.65 mmol) of the methanesulfonate 7, and the mixture
Reaction of the Alcohol 8 with LiAlH4.
A mixture of
was stirred for 2 h. The mixture was poured into water, and the
organic layer was washed with aq NH4Cl and dried over MgSO4.
Column chromatography through silica gel with dichlorometh-
ane–hexane (3:1) as the eluent afforded 110 mg (0.30 mmol, 46%)
50.0 mg (0.089 mmol) of compound 8 and 38 mg (1.0 mmol) of
LiAlH4 in 10 mL of THF was heated under reflux for 24 h. After
removal of the solvent, the residue was partitioned with water and
dichloromethane. The organic layer was washed with water and
ꢁ
1
of compound 3, mp 144–146 C. Found: C, 94.48; H, 5.72%.
1
dried over MgSO4, and the solvent was evaporated. H NMR
Calcd for C29H20: C, 94.53; H, 5.47%. H NMR (CDCl3) ꢀ 5.407
spectrum of the residue showed mostly the signals of the unreact-
ed 8 together with signals ascribable to a trace amount of 1,3-di(9-
triptycyl)-2-propen-1-ol (11) (see below).
0
(
6
1H, s, 10-H), 6.667 (1H, d, J ¼ 6:9 Hz, 3 -H), 6.896 (1H, d, J ¼
0
:9 Hz, 1 -H), 6.95–7.03 (6H, m), 7.27 (1H, m, p-H), 7.35–7.43
(
1
(
5H, m, 4/5/16-H, m-H), 7.53 (2H, m, o-H), 7.71 (3H, m, 1/8/
3-H). 13C NMR (CDCl3) ꢀ 54.19 (1C, t), 54.29 (1C, q), 91.20
1C, t), 97.25 (1C, t), 122.36 (3C, t), 123.51 (3C, t), 124.94 (3C,
t), 125.30 (3C, t), 127.24 (2C, t), 127.36 (1C, t), 128.85 (2C, t),
33.99 (1C, q), 145.81 (3C, q), 145.84 (3C, q), 207.69 (1C, q).
,3-Di(9-triptycyl)propadiene (4). To a suspension of 1.00 g
3.00 mmol) of 9-bromotriptycene in 25 mL of dry diethyl ether
1,3-Di(9-triptycyl)-2-propynyl Acetate (9). A mixture of
50.0 mg (0.089 mmol) of compound 8, 3.0 mL (32 mmol) of acetic
anhydride, and 1.0 mL (12 mmol) of pyridine was stirred for 24 h
at room temperature. The mixture was poured onto ice-water and
extracted with dichloromethane. The extracts were washed with
water and dried over MgSO4, and the solvent was evaporated. Re-
crystallization of the residue from dichloromethane–hexane gave
1
1
(
ꢁ
was added at room temperature 3.44 mL (5.30 mmol) of a 1.54 M
solution of butyllithium in hexane and the mixture was stirred for
4
freshly distilled benzene was added to afford a solution of 9-tri-
ptycyllithium. The solution was added to a suspension of 300 mg
39.2 mg (0.065 mmol, 73%) of compound 9, mp 189–191 C.
Found: C, 89.97; H, 5.31%. Calcd for C45H30O2: C, 89.67; H,
1
h. The supernatant diethyl ether was decanted off, and 120 mL of
5.02%. H NMR (CDCl3) ꢀ 2.367 (3H, s), 5.363 (1H, s), 5.455
(1H, s), 6.93–7.19 (13H, m), 7.339 (3H, m), 7.40–7.47 (2H, m),
7.499 (1H, s), 7.518 (1H, m), 7.662 (3H, m), 8.156 (1H, m),
13
(
1.56 mmol) of well-dried copper(I) iodide in 18 mL of diethyl
8.524 (1H, m). C NMR (CDCl3) ꢀ 21.39 (1C, p), 53.26 (1C, t),
53.30 (1C, q), 54.54 (1C, t), 57.10 (1C, q), 63.84 (1C, t), 84.86
(1C, q), 88.68 (1C, q), 121.34 (1C, t), 122.77 (3C, t), 123.33
(3C, t), 123.40 (1C, t), 123.66 (1C, t), 123.71 (1C, t), 123.82
(1C, t), 124.51 (1C, t), 124.65 (1C, t), 125.10 (4C, t), 125.29
(1C, t), 125.57 (1C, t), 125.65 (3C, t), 125.74 (1C, t), 125.80
(1C, t), 141.41 (1C, q), 143.27 (1C, q), 144.02 (1C, q), 144.16
ether, and the mixture was stirred at room temperature for 1 h.
To the mixture was added a solution of 150 mg (0.390 mmol) of
compound 7 in 6 mL of diethyl ether and the mixture was stirred
for 2 h. The mixture was poured into ice-water, and the organic
layer was washed with aq NH4Cl and dried over MgSO4. Column
chromatography through silica gel with dichloromethane–hexane

1
298 Bull. Chem. Soc. Jpn. Vol. 79, No. 8 (2006)
9-Triptycylallenes
(
(
3C, q), 144.22 (3C, q), 145.65 (1C, q), 146.94 (1C, q), 147.18
1C, q), 170.53 (1C, q).
88.79 (1C, q), 121.94 (1C, t), 122.46 (3C, t), 123.14 (1C, t),
123.54 (3C, t), 123.78 (1C, t), 123.81 (1C, t), 123.85 (1C, t),
124.57 (1C, t), 124.66 (1C, t), 125.21 (4C, t), 125.34 (1C, t),
125.45 (1C, t), 125.74 (1C, t), 125.88 (3C, t), 125.93 (1C, t),
140.52 (1C, q), 142.64 (1C, q), 143.09 (1C, q), 143.84 (3C, q),
144.14 (3C, q), 145.50 (1C, q), 146.88 (1C, q), 146.97 (1C, q).
1,3-Di(9-triptycyl)propyne (12). To a solution of 200 mg
(0.313 mmol) of compound 10 in 15 mL of anhydrous THF was
added 114 mg (3.0 mmol) of LiAlH4, and the mixture was heated
under reflux for 24 h. The reaction mixture was poured onto ice-
water and extracted with dichloromethane. The extracts were
washed with brine and dried over MgSO4, and the solvent was
evaporated. Recrystallization of the residue from dichlorometh-
ane–hexane gave 130 mg (0.239 mmol, 76%) of 12, mp 299–
Reaction of the Acetate 9 with LiAlH4. A mixture of 100 mg
0.166 mmol) of compound 9 and 57 mg (1.5 mmol) of LiAlH4 in
(
1
0 mL of THF was heated under reflux for 24 h. After removal of
the solvent, the residue was partitioned by water and dichloro-
methane. The organic layer was washed with water and dried over
MgSO4, and the solvent was evaporated. Recrystallization of the
residue from dichloromethane–hexane gave 54 mg (0.096 mmol,
1
5
8%) of a solid, which was guessed by H NMR to be (E)-1,3-
ꢁ
di(9-triptycyl)-2-propen-1-ol (11), mp 335–336 C. 1H NMR
(
(
7
7
CDCl3) ꢀ 2.859 (1H, d, J ¼ 4:1 Hz, OH), 5.422 (1H, s), 5.436
1H, s), 6.496 (1H, ddd, J ¼ 6:6, 4.1, 1.1 Hz), 6.93–7.09 (10H, m),
.136 (1H, td, J ¼ 7:5, 1.4 Hz), 7.356 (1H, dd, J ¼ 16:7, 6.6 Hz),
.38–7.45 (6H, m), 7.491 (1H, dd, J ¼ 7:1, 1.4 Hz), 7.709 (3H,
ꢁ
300 C. Found: C, 95.20; H, 5.15%. Calcd for C43H28: C, 94.82;
1
m), 7.776 (1H, dd, J ¼ 16:7, 1.1 Hz), 7.795 (1H, m), 7.958 (1H, d,
J ¼ 7:4 Hz), 8.116 (1H, d, J ¼ 7:2 Hz).
H, 5.18%. H NMR (CDCl3) ꢀ 4.366 (2H, s), 5.367 (1H, s), 5.474
(1H, s), 6.91–7.10 (12H, m), 7.339 (3H, m), 7.447 (3H, m), 7.692
(3H, m), 7.93 (3H, br s). 13C NMR (CDCl3) ꢀ 19.42 (1C, s), 52.66
(1C, q), 53.24 (1C, t), 53.52 (1C, q), 54.25 (1C, t), 79.66 (1C, q),
89.85 (1C, q), 122.21 (3C, br t), 122.78 (3C, t), 123.25 (3C, t),
123.56 (3C, t), 124.83 (3C, t), 125.01 (3C, t), 125.31 (3C, t),
125.49 (3C, t), 144.37 (3C, q), 144.78 (3C, q), 144.9 (3C, br q),
146.60 (3C, q).
X-ray Crystallography. Crystals of compounds 1 and 3 were
grown from diethyl ether–hexane, those of compound 4 were
grown from ethyl acetate–hexane, and those of compound 12 were
grown from chloroform. The crystal data and the parameters for
data collection, structure determination, and refinement are sum-
marized in Table 4. Diffraction data were collected on a Rigaku
AFC7R or a Rigaku/MSC Mercury CCD diffractometer, and cal-
culations were performed using the SHELXL97 program.14 The
structures were solved by direct methods followed by full-matrix
least-squares refinement with all non-hydrogen atoms anisotropic
and all hydrogen atoms isotropic. Reflection data with jIj >
2:0ꢁðIÞ were used.
1,3-Di(9-triptycyl)-2-propynyl Methanesulfonate (10). To a
solution of 2.00 g (3.57 mmol) of compound 8 in 40 mL of dry
ꢁ
THF was added at 0 C under argon 2.70 mL (4.20 mmol) of
1
1
sulfonyl chloride, and the mixture was stirred for 24 h at room
temperature. The reaction mixture was poured onto ice-water
and extracted with dichloromethane. The extracts were washed
with brine and dried over MgSO4, and the solvent was evaporated.
Recrystallization of the residue from dichloromethane–hexane af-
.59 M butyllithium in hexane, and the mixture was stirred for
h. To the mixture was added 0.53 mL (6.85 mmol) of methane-
ꢁ
forded 1.76 g (2.76 mmol, 77%) of compound 10, mp 290–291 C
(
dec). Found: C, 82.83; H, 5.18%. Calcd for C44H30O3S: C, 82.73;
1
H, 4.73%. H NMR (CDCl3) ꢀ 3.458 (3H, s), 5.375 (1H, s), 5.451
1H, s), 6.91–7.17 (12H, m), 7.354 (3H, dd, J ¼ 6:9, 1.5 Hz),
.40–7.48 (2H, m), 7.432 (1H, s), 7.510 (1H, m), 7.656 (3H, dd,
(
7
J ¼ 7:1, 1.5 Hz), 7.704 (1H, d, J ¼ 7:2 Hz), 8.015 (1H, m), 8.454
(
(
1H, m). 13C NMR (CDCl3) ꢀ 40.70 (1C, p), 53.22 (1C, t), 53.40
1C, q), 54.48 (1C, t), 57.51 (1C, q), 70.25 (1C, t), 86.84 (1C, q),
Table 4. Crystal Data and Parameters for Data Collection, Structure Determination, and Refinement
Compound
1
3
4
12
Empirical formula
Formula weight
Crystal system
Space group
C23H16
292.38
triclinic
C29H20
C43H28 C4H8O2
C43H28 CHCl3
664.07
triclinic
ꢆ
ꢆ
368.48
monoclinic
P21=a
632.80
triclinic
ꢁ
P1
ꢁ
P1
ꢁ
P1
˚
a/A
8.278(1)
13.187(1)
8.162(1)
94.45(1)
113.91(1)
73.91(1)
782.1(1)
2
1.242
0.070
293(2)
55.0
9.263(1)
13.059(2)
16.959(1)
90.00
97.05(1)
90.00
2036.0(4)
4
1.202
0.068
293(2)
55.0
8.716(2)
11.749(3)
17.803(4)
87.05(1)
76.91(1)
89.50(1)
1773.4(7)
2
1.185
0.071
100(2)
55.0
8.465(3)
12.658(3)
17.149(4)
65.07(1)
77.73(1)
88.22(1)
1624.7(8)
2
1.355
0.314
100(2)
54.5
˚
b/A
˚
c/A
ꢂ/
ꢁ
ꢁ
ꢃ/
ꢁ
ꢄ/
V/A
˚
3
Z
ꢄ3
Dcalcd/g cm
ꢅ(Mo Kꢂ)/cm
Temp/K
2ꢆmax/
No. of reflections measured
ꢄ1
ꢁ
Total
Unique
3601
2946
4665
2278
6619
4960
6909
5409
No. of refinement variables
aÞ
208
0.0450; 0.1187
1.058
262
0.0479; 0.1191
1.112
554
0.0665; 0.1921
1.080
424
0.0784; 0.1348
1.357
bÞ
Final R1; wR2
GOF
2
2
2 2 1=2
a) R1 ¼ ꢂjjFoj ꢄ jFcjj=ꢂjFoj. b) wR2 ¼ fꢂ½wðFo ꢄ Fc Þꢇ=ꢂ½wðFo Þ ꢇg
.

G. Yamamoto et al.
Bull. Chem. Soc. Jpn. Vol. 79, No. 8 (2006) 1299
Crystallographic data have been deposited with Cambridge
Crystallographic Data Centre: Deposition numbers CCDC-
J. Org. Chem. 1989, 54, 3726.
E. C. Kornfeld, P. Barney, J. Blankley, W. Faul, J. Med.
Chem. 1965, 8, 342.
5
6
04410 to CCDC-604413 for compounds 1, 3, 4, and 12, respec-
tively. Copies of the data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cam-
bridge Crystallographic Data Centre, 12, Union Road, Cambridge,
CB2 1EZ, UK; Fax: +44 1223 336033; e-mail: deposit@ccdc.
cam.ac.uk).
6
1582.
7
E. I. Snyder, J. D. Roberts, J. Am. Chem. Soc. 1962, 84,
J. K. Crandall, S. A. Sojka, J. Am. Chem. Soc. 1972, 94,
13
5084; E. Breitmeier, W. Voelter, C NMR Spectroscopy, VCH,
Weinheim, New York, 1978, p. 141.
¯
See for example: M. Oki, The Chemistry of Rotational
8
¯
Isomers, Springer Verlag, Berlin, 1993; M. Oki, Applications of
Dynamic NMR Spectroscopy to Organic Chemistry, VCH, New
York, 1985, Chapt. 5.
¯
9 F. Suzuki, M. Oki, H. Nakanishi, Bull. Chem. Soc. Jpn.
1974, 47, 3114.
References
1
Modern Allene Chemistry, ed. by N. Krause, A. S. K.
Hashmi, Wiley-VCH, Weinheim, 2004.
For our recent studies on stereochemistry of triptycene
2
derivatives, see: G. Yamamoto, S. Ohta, M. Kaneko, K. Mouri,
M. Ohkuma, R. Mikami, Y. Uchiyama, M. Minoura, Bull. Chem.
Soc. Jpn. 2005, 78, 487; C. Agawa, K. Otsuka, M. Minoura, Y.
Mazaki, G. Yamamoto, Bull. Chem. Soc. Jpn. 2004, 77, 2273.
10 G. Yamamoto, Tetrahedron 1990, 46, 2761.
11 Y. K. Grishin, N. M. Sergeev, O. A. Subbotin, Y. A.
Ustynyuk, Mol. Phys. 1973, 25, 297.
12 F. M. Logullo, A. H. Seitz, L. Friedman, Org. Synth. 1973,
Coll. Vol. V, 54.
3
H. Iwamura, J. Mol. Struct. 1985, 126, 401; H. Iwamura,
¯
13 S. Toyota, T. Yamamori, M. Asakura, M. Oki, Bull. Chem.
K. Mislow, Acc. Chem. Res. 1988, 21, 175; K. Mislow, Chem-
tracts: Org. Chem. 1989, 2, 151.
4 See for example: J. K. Crandall, D. J. Keyton, J. Kohne,
J. Org. Chem. 1968, 33, 3655; C. J. Elsevier, P. Vermeer,
Soc. Jpn. 2000, 73, 205.
14 G. M. Sheldrick, SHELXL97, Program for the Refinement
of Crystal Structures, University of G o¨ ttingen, Germany, 1997.