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Synthesis, properties and reduction of 1,8-naphthylenebis(diphenylcyclopropenium) dication
Tetrahedron Letters,Vol.23,No.l,pp 91-94,1982 Printed in Great Britain
SYNTHESIS,
PROPERTIES,
0040-4039/82/[email protected]/0 01982 Pergamon Press Ltd.
AND REDUCTION
1,8-NAPHTHYLENEBIS(DIPHENYLCYCLOPROPENIUM)
Koichi KOMATSU, Department
OF DICATION
')
Mikiro ARAI, and Kunio OKAMOTO*
of Hydrocarbon
Kyoto University,
Chemistry, Sakyo-ku,
Faculty of Engineering, Kyoto 606, Japan
Abstract: Synthesis, properties, and the result of one-electron reduction are described for the title compound, which is the first example of the stable dication containing two cationic rings in a close face-to-face arrangement.
Various
types of carbocyclic
have been subjected nonbenzenoid
aromatic
novel property
cation
as a strong a-acceptor
due to the extreme
paper we wish to report on the synthesis stable dication The properties
with two positive will be discussed
at remote positions,
dication
have not allowed present
of the title compound
rings fixed in a face-to-face
the structurally
(diphenylcyclopropenium)
to the dication
related monocations
(2) reported
interest
As a matter
r-systems
those having a because of their of course,
analogs which have two positively
inevitably
with reference
interacting
Especially
are of current
but such species
instability
intramolecularly studies.
CT complexes. 2,
the dicationic
fixed in close proximity,
investigation
containing
and theoretical
as a new type of intramolecular
have also been made to synthesize n-systems
compounds
to both synthetic
isolation
attempts
charged
nor spectral
in such systems. 3,
In this
(1) as the first example conformation
of the
at close location.
,2 having the two cationic
rings
3 and 4, and the p-phenylenebis-
by Either aid Berieth.4)
Ph
Ph
0 P Ph The syntheses compounds
by succeeding
reactions,
recrystallization isolated
utilized
the addition
as shown in Scheme
(C6H6/Si02),
from CHC13- n-C6H14
respectively; cation
of phenylchlorocarbene
The intramolecular
was isolated
by crystallization
corresponding
1.
to respective
dicyclopropenyl
+
acetylenic
ether _6,5) which was formed
by the use of PTLC (C6H6-n-C6H14(2:l)/Si02)
followed
, while the covalent chlorocyclopropenes,
from CH2C12 -MeCN,
preparative
then, the cyclopropenes
salts by treatment
were converted
with Ph3C'BF4-.
91
HPLC
5
Ph -
by
7, 8, and 9 were . . (C6H14/microporasil), and"PTLC quantitatively
into the
92
Scheme
1
Ph
Ph
I;, IL
PhCHC12-t-BuOK6) C~;6 ,:,I"
,
P
Ph Ph
h
[ 'w
]
-Qph
' ';;;;y, 5
X= Cl-t-BuO
'.2BF4 98%
32%; yellow powder mp 173.5-174.3'
OH-
2 Ph3C+BF4Ph
7
,lr
>
MeCN-CH2C12
67%; yellow powder mp 250.3-251"
2. 2BF494%
Ph3C+BF4-
III p;1
,8 16%; yellow
III Ph III
>
MeCN
oil
3. BF4100%
Ph.& cl' 'N
Ph3C+BF4>
-----GG CgH6 '
Table 1. Physical
Compd
and Spectral
IR v(KBr) -1 cm
1 . 2BF4.,
Yellow tryst. mp 250.4-252"
4. BF4_ White tryst. mp 239.5-241"
Properties
uv XMeCN max nm (log E)
of the Tetrafluoroborates
'H NMR (220 MHz) 6 (Ca3CN) ppm Ph
4. BF4_ g5%
MeCN-CH2C12
oil
of
1, 2, 3, and 4 a
_
.
..,
13C NMR 6 (CD3CN)
Naph
Ph
V7
..,
ppm Naph
244 303 377 393
(4.55) (4.67) (4.33) (4.31)
8.04 (0) 9.03 (H-2) 7.76(p) 8.97(H-4) 7.63(m) 8.31 (H-3)
154.5b 154.0c
139.6(p) 136.4 (m) 131.1 (0) 119.0 (i)
141.5(C-2) 140.5 (C-4) 135.4(C-4a) 131.7(C-aa) 129.2 (C-3) 129.O(C-1)
1415 vs 1060 b,vs
240 261 286 301 365 383
(4.62) (4.60) (4.62) (4.64) (4.55) (4.54)
a.59 (o) a.97 (~-2) 8.08 (p) a.73 (~-4) 7.95 (m) a.24 (H-3) (100 MHz)-
159.0b 155.3c
140.1 (p) 137.1 (m) 131.7 (0) 121.1 (i)
138.1 135.2 132.9 130.5 121.2
2220 w 1395 vs 1055 b,vs
230 254 297 392
(4.56) (4.49) (4.61) (4.21)
Paleyellow tryst. mp 307.5-310" 3. BF4_
34%; pale-yellow
1410 vs 1060 b,vs
Paleyellow tryst. mp 227-229.7" 2. 2BF4..,
9
1420 vs 1060 b.vs
213 (4.79) 261 (4.38) 285 (4.42) 33ashi4.20j 361 (4.27)
a) All the salts gave satisfactory
(c-2) (C-4) (C-4a) (C-3). (C-l)
139.6 (p) 138.0 137.8 136.9 (m) 134.3 133.2 131.6 (0) 130.5 130.4
a.53 (o) 8.78 (~-2) 8.07 (p) 8.60 (H-4) 7.90 (m) 8.2-7.8 (H-3,%8)
elemental
analyses.
b)
157.8 b 155.4c
139.4 (p) 140.1 137.8 136.8(m) 134.7 132.6 131.5 (0) 131.0 130.9 121.3 (i) 129.2 127.0 125.9 119.0
Ph ')
xh
93
All of the new tetrafluoroborate properties
listed in Table 1.
phenyl protons demonstrating conformation
in l as compared
with those in ,2 (A6 0.55(o),
the ring current
for the naphthalene
rigid molecules
containing
by the dominating appreciable
rings in 1. 7,
of the cyclopropenium ring carbons
crowded
IT-TIcompression
shielding
lene carbons
a-systems,
charge, which was locally
accumulated
placed two three-membered
rings,
inductively
ring through
into the neutral
of two cationic rings
mity should result of the dicationic the results
Cation
destabilization
of pKR+ measurements
Actually,
given in Table 2
(as in the dication
lization
due to the electrostatic
cationic
rings closely
repulsion
facing each other.
of the
‘d
y
-0.42 '
-0.75
(l.78)d
111 PhPh
(_3)
1.16
-1.04
(!)
1.62
-1.07
Ph
(-1.32) is
(!!),g)
(10) and tetra."W it is supposed that by the
electronic
rings
interaction
the u-bond
in 1 is caused ., of the two cationic
of the naphthalene
of the through-space
framework interaction
is
small.
On the other hand, the dication than the p-phenylene-type
2 is less * dication
5 4, reflecting less a-conjugative interaction ..' between the two positive rings across the 1,5naphthylene
(l.ll)d
Since a
most of the destabilization
destabilized
Ph
-0.54
the trimethylene-
methylene-dications
and the effect
Ph
-2.08'
1) as
(as in the
amount of pKR+ difference
between
b ERed'n V vs Ag/Ag+
of the second cyclopropenium
with that at the 5-position
relatively
Potentials
PKR+ a
(1)
is brought
2). The pKR+ difference between 1 and 2, .., .W amounts to -1.66, is ascribed to the destabi-
through
"leaking
Ph PhPh Ph
dication
observed
and naphtha-
due to slight
pK,+ and Reduction
at such close proxi-
in considerable
ring at the 8-position
comparable
densities
Table 2.
then, that the
system as a whole.
about by introduction
which
is known to be obscured
for the cyclopropenium
in charge
naphthalene
reveal that the marked destabilization
compared
shift is
In 13C NMR spectra of
the u-framework.
It may well be anticipated, presence
effect
shift is also
the downfield
and 1).
clearly
the face-to-face
in the present case, the small but
respectively
to a change
upfield
in 1, while
the ring current
out" of the dipositive at closely
The similar
C-2,4,4a:
Therefore,
observed
be ascribed
ring and thereby
carbons
(especially
effect.*)
and deshielding
should rather
0.32 (m), and 0.32 (p)ppm),
effect of the facing benzene
of two diphenylcyclopropenium
noted for the l3C NMR signals observed
salts of l-4 are stable under air, and exhibit the W.. is the apparent upfield shift of the 'H NMR signals of
Noteworthy
system.
a)Measured spectrophotometrically in 50%b)CV peak potential at scan rate aq.MeCN. of O.lV/sec in MeCN with TBAP (O.lM). c) Measured in dil.H2SO4-EtOH by the use of Co function calibrated with (p-MeOC6H4)2PhCt according to N.C.Deno et al.,J.Am.Chem. s0~.,&2367(1961). d)Value for the second neutralization. e)Ref. 4. f)Ref. 9.
94
The values of reduction
indicating
to that for pKR+ values, reduction.
potential
Thus, the chemical
the greatest
reduction
7,8,9,10-tetraphenylfluoranthene formation
also given in Table 2 exhibit
of 1,8-naphthylenebis(diphenylcyclopropenyl),
bicyclopropenyl+benzene as an intermediate Scheme ,
rearrangement
according
trend similar
susceptibility
of 1 with excessive
10) as a single product,
1,8-naphthylenebis(diphenylcyclopropeny1)
the general
diradical,
of 1 towards one-electron * zinc powder smoothly afforded
most probably
by way of the initial
the intramolecular as shown in Scheme
may involve a highly strained
to the recent mechanistic
coupling
2.
Dewar benzene
or benzvalene
studies. 11)
2 Me;;, rtl
[PhgPho;hgph]
Rearr;p$$
80%; mp 312-313.5" References
product of
The subsequent
10)
and Notes:
‘I
The One-Electron Reduction of Carbonium Ions.15. For part 14, see K. Takeuchi, T. Kurosaki, Y. Yokomichi, Y. Kimura, Y. Kubota, H. Fujimoto, and K. Okamoto, J.C.S.Perkin II, 1981, 670.
2)
Horita,T. Otsubo, Y. a)J.G.O'Connor and P.M. Keehn, J.Am. Chem.soc., %,8446(1976);b)H. Sakata,and S.Misumi, Tetrahedron Lett., 1976, 3899;c) J. G. O'Connorand P.M.Keehn, ibid.,= e) H. Horita,T.Otsubo, and 3711; d)T. Nakazawaand I. Murata, J.Am. Chem. sot., 2,1996(1977); f)D. N. Butler and I. Gupta,cah. J. Chem., 56,80 (1978); g) K. S. Misumi, Chem. L&t., 1978,807; Komatsu, N.Abe, K. Takahashi, and K. Okamoto,J. Orq.Chem.,s, 2712 (1979);v K. Komatsu, K. Nakazawa,N. Abe,K. Kubo,and I. Takahashi, and K. Okamoto,retrahedron Lett., =,4747;i)T. !-%.Wata,ibid., m,4995;j) K. Yamamura,K. Nakatsu, K. Nakao,T. Nakazawa,and I. Murats, ibid., =,4999;k)T.Nakazawa,Y.Niimoto,K.Kubo, andI. Murata,nngew. Chem.,z, 566 (1980).
dication (Ref. 2c) nor that to 3) Neither an attempt to isolate [2.2](1,4)tropylioparacyclophane isolate 1,8-ditropylionaphthalene dication was successful due to rapid decomposition: K. Komatsu, N. Abe, and K. Okamoto, unpublished result. 4) T. Either and H. Berneth,
Tetrahedron
Lett.,
1973, 2039.
5) Also formed by complete neutralization of 1: IR v (KBr) 1800(m), 1125(m), 1100(m) trn-', UV h,, (MeCN) 230 nm (log E, 4.64), 247 (4.61), 314 (4.38), 328 (4.38), 350 (4.26); H NMR (220 MHz) 6 (CDC13) 8.26 (d, 2H, Naph-H-2), 7.91 (d, 2H, Naph-H-4), 7.87 (d, 4!, o-H), 7.60 (t, 2H, Naph-H-3), 7.46 (m, 6H, m,~-H), 7.17 (d, $1, O-H'), 6.97 (m, 6H, m,p-H A; 13C NMR 6 (CDC13) 144.1-124.2 (14 peaks, Ar-C), 119.2 (Kf ), 117.‘9 (qNaph), 65.8 (;,a); Anal. Calcd for C40H260:C, 91.92; H, 5.01%. Found:C, 91.52;H, 5.07%. 6) This method is similar to the one used for the synthesis of 5 (Ref. 4). The use of phenylchlorodiazirine as the carbene generator was found unsuitable becauseofthe instability of the first formed mono-carbene-adductunder the reaction conditions leading to a complexmixture of byproducts. 7) A comparable amount of upfield shift (A6 0.53)is observed for the facing phenyl protons in 1,8diphenylnaphthalene: H. 0. House, R. W. Magin, and.H. W.Thompson, J. org. Chem., Z&2403 (1963). 8) For example, see T. Kaneda, T. Otsubo, H. Horita, 1015 (1980), for the case of [n.n]paracyclophanes. 9) K. Komatsu, K. Masumoto, and K. Okamoto, Abstracts Aromatic Compounds (Sendai), p.23 (1976). 10) Lit. mp 312-314":
K. Rasheed,
Tetrahedron,
21,
and S. Misumi,~ull.
Chem.soc.Jpn.,
for the 9th Symposium
3,
on Nonbenzenoid
2957 (1966).
L&t., 1974, 11) For example, I. J. Landheer, W. H. de Wolf, and F. Brickelhaupt, Tetrahedron 2813, ibid., __ 1975, 349; J. H. Davis, K. J. Shea, and R. G. Bergman, Angew. Chem., 88, 254 (1976), and the references cited therein.
(Received in Japan 14 September 1981)
SYNTHESIS,
PROPERTIES,
0040-4039/82/[email protected]/0 01982 Pergamon Press Ltd.
AND REDUCTION
1,8-NAPHTHYLENEBIS(DIPHENYLCYCLOPROPENIUM)
Koichi KOMATSU, Department
OF DICATION
')
Mikiro ARAI, and Kunio OKAMOTO*
of Hydrocarbon
Kyoto University,
Chemistry, Sakyo-ku,
Faculty of Engineering, Kyoto 606, Japan
Abstract: Synthesis, properties, and the result of one-electron reduction are described for the title compound, which is the first example of the stable dication containing two cationic rings in a close face-to-face arrangement.
Various
types of carbocyclic
have been subjected nonbenzenoid
aromatic
novel property
cation
as a strong a-acceptor
due to the extreme
paper we wish to report on the synthesis stable dication The properties
with two positive will be discussed
at remote positions,
dication
have not allowed present
of the title compound
rings fixed in a face-to-face
the structurally
(diphenylcyclopropenium)
to the dication
related monocations
(2) reported
interest
As a matter
r-systems
those having a because of their of course,
analogs which have two positively
inevitably
with reference
interacting
Especially
are of current
but such species
instability
intramolecularly studies.
CT complexes. 2,
the dicationic
fixed in close proximity,
investigation
containing
and theoretical
as a new type of intramolecular
have also been made to synthesize n-systems
compounds
to both synthetic
isolation
attempts
charged
nor spectral
in such systems. 3,
In this
(1) as the first example conformation
of the
at close location.
,2 having the two cationic
rings
3 and 4, and the p-phenylenebis-
by Either aid Berieth.4)
Ph
Ph
0 P Ph The syntheses compounds
by succeeding
reactions,
recrystallization isolated
utilized
the addition
as shown in Scheme
(C6H6/Si02),
from CHC13- n-C6H14
respectively; cation
of phenylchlorocarbene
The intramolecular
was isolated
by crystallization
corresponding
1.
to respective
dicyclopropenyl
+
acetylenic
ether _6,5) which was formed
by the use of PTLC (C6H6-n-C6H14(2:l)/Si02)
followed
, while the covalent chlorocyclopropenes,
from CH2C12 -MeCN,
preparative
then, the cyclopropenes
salts by treatment
were converted
with Ph3C'BF4-.
91
HPLC
5
Ph -
by
7, 8, and 9 were . . (C6H14/microporasil), and"PTLC quantitatively
into the
92
Scheme
1
Ph
Ph
I;, IL
PhCHC12-t-BuOK6) C~;6 ,:,I"
,
P
Ph Ph
h
[ 'w
]
-Qph
' ';;;;y, 5
X= Cl-t-BuO
'.2BF4 98%
32%; yellow powder mp 173.5-174.3'
OH-
2 Ph3C+BF4Ph
7
,lr
>
MeCN-CH2C12
67%; yellow powder mp 250.3-251"
2. 2BF494%
Ph3C+BF4-
III p;1
,8 16%; yellow
III Ph III
>
MeCN
oil
3. BF4100%
Ph.& cl' 'N
Ph3C+BF4>
-----GG CgH6 '
Table 1. Physical
Compd
and Spectral
IR v(KBr) -1 cm
1 . 2BF4.,
Yellow tryst. mp 250.4-252"
4. BF4_ White tryst. mp 239.5-241"
Properties
uv XMeCN max nm (log E)
of the Tetrafluoroborates
'H NMR (220 MHz) 6 (Ca3CN) ppm Ph
4. BF4_ g5%
MeCN-CH2C12
oil
of
1, 2, 3, and 4 a
_
.
..,
13C NMR 6 (CD3CN)
Naph
Ph
V7
..,
ppm Naph
244 303 377 393
(4.55) (4.67) (4.33) (4.31)
8.04 (0) 9.03 (H-2) 7.76(p) 8.97(H-4) 7.63(m) 8.31 (H-3)
154.5b 154.0c
139.6(p) 136.4 (m) 131.1 (0) 119.0 (i)
141.5(C-2) 140.5 (C-4) 135.4(C-4a) 131.7(C-aa) 129.2 (C-3) 129.O(C-1)
1415 vs 1060 b,vs
240 261 286 301 365 383
(4.62) (4.60) (4.62) (4.64) (4.55) (4.54)
a.59 (o) a.97 (~-2) 8.08 (p) a.73 (~-4) 7.95 (m) a.24 (H-3) (100 MHz)-
159.0b 155.3c
140.1 (p) 137.1 (m) 131.7 (0) 121.1 (i)
138.1 135.2 132.9 130.5 121.2
2220 w 1395 vs 1055 b,vs
230 254 297 392
(4.56) (4.49) (4.61) (4.21)
Paleyellow tryst. mp 307.5-310" 3. BF4_
34%; pale-yellow
1410 vs 1060 b,vs
Paleyellow tryst. mp 227-229.7" 2. 2BF4..,
9
1420 vs 1060 b.vs
213 (4.79) 261 (4.38) 285 (4.42) 33ashi4.20j 361 (4.27)
a) All the salts gave satisfactory
(c-2) (C-4) (C-4a) (C-3). (C-l)
139.6 (p) 138.0 137.8 136.9 (m) 134.3 133.2 131.6 (0) 130.5 130.4
a.53 (o) 8.78 (~-2) 8.07 (p) 8.60 (H-4) 7.90 (m) 8.2-7.8 (H-3,%8)
elemental
analyses.
b)
157.8 b 155.4c
139.4 (p) 140.1 137.8 136.8(m) 134.7 132.6 131.5 (0) 131.0 130.9 121.3 (i) 129.2 127.0 125.9 119.0
Ph ')
xh
93
All of the new tetrafluoroborate properties
listed in Table 1.
phenyl protons demonstrating conformation
in l as compared
with those in ,2 (A6 0.55(o),
the ring current
for the naphthalene
rigid molecules
containing
by the dominating appreciable
rings in 1. 7,
of the cyclopropenium ring carbons
crowded
IT-TIcompression
shielding
lene carbons
a-systems,
charge, which was locally
accumulated
placed two three-membered
rings,
inductively
ring through
into the neutral
of two cationic rings
mity should result of the dicationic the results
Cation
destabilization
of pKR+ measurements
Actually,
given in Table 2
(as in the dication
lization
due to the electrostatic
cationic
rings closely
repulsion
facing each other.
of the
‘d
y
-0.42 '
-0.75
(l.78)d
111 PhPh
(_3)
1.16
-1.04
(!)
1.62
-1.07
Ph
(-1.32) is
(!!),g)
(10) and tetra."W it is supposed that by the
electronic
rings
interaction
the u-bond
in 1 is caused ., of the two cationic
of the naphthalene
of the through-space
framework interaction
is
small.
On the other hand, the dication than the p-phenylene-type
2 is less * dication
5 4, reflecting less a-conjugative interaction ..' between the two positive rings across the 1,5naphthylene
(l.ll)d
Since a
most of the destabilization
destabilized
Ph
-0.54
the trimethylene-
methylene-dications
and the effect
Ph
-2.08'
1) as
(as in the
amount of pKR+ difference
between
b ERed'n V vs Ag/Ag+
of the second cyclopropenium
with that at the 5-position
relatively
Potentials
PKR+ a
(1)
is brought
2). The pKR+ difference between 1 and 2, .., .W amounts to -1.66, is ascribed to the destabi-
through
"leaking
Ph PhPh Ph
dication
observed
and naphtha-
due to slight
pK,+ and Reduction
at such close proxi-
in considerable
ring at the 8-position
comparable
densities
Table 2.
then, that the
system as a whole.
about by introduction
which
is known to be obscured
for the cyclopropenium
in charge
naphthalene
reveal that the marked destabilization
compared
shift is
In 13C NMR spectra of
the u-framework.
It may well be anticipated, presence
effect
shift is also
the downfield
and 1).
clearly
the face-to-face
in the present case, the small but
respectively
to a change
upfield
in 1, while
the ring current
out" of the dipositive at closely
The similar
C-2,4,4a:
Therefore,
observed
be ascribed
ring and thereby
carbons
(especially
effect.*)
and deshielding
should rather
0.32 (m), and 0.32 (p)ppm),
effect of the facing benzene
of two diphenylcyclopropenium
noted for the l3C NMR signals observed
salts of l-4 are stable under air, and exhibit the W.. is the apparent upfield shift of the 'H NMR signals of
Noteworthy
system.
a)Measured spectrophotometrically in 50%b)CV peak potential at scan rate aq.MeCN. of O.lV/sec in MeCN with TBAP (O.lM). c) Measured in dil.H2SO4-EtOH by the use of Co function calibrated with (p-MeOC6H4)2PhCt according to N.C.Deno et al.,J.Am.Chem. s0~.,&2367(1961). d)Value for the second neutralization. e)Ref. 4. f)Ref. 9.
94
The values of reduction
indicating
to that for pKR+ values, reduction.
potential
Thus, the chemical
the greatest
reduction
7,8,9,10-tetraphenylfluoranthene formation
also given in Table 2 exhibit
of 1,8-naphthylenebis(diphenylcyclopropenyl),
bicyclopropenyl+benzene as an intermediate Scheme ,
rearrangement
according
trend similar
susceptibility
of 1 with excessive
10) as a single product,
1,8-naphthylenebis(diphenylcyclopropeny1)
the general
diradical,
of 1 towards one-electron * zinc powder smoothly afforded
most probably
by way of the initial
the intramolecular as shown in Scheme
may involve a highly strained
to the recent mechanistic
coupling
2.
Dewar benzene
or benzvalene
studies. 11)
2 Me;;, rtl
[PhgPho;hgph]
Rearr;p$$
80%; mp 312-313.5" References
product of
The subsequent
10)
and Notes:
‘I
The One-Electron Reduction of Carbonium Ions.15. For part 14, see K. Takeuchi, T. Kurosaki, Y. Yokomichi, Y. Kimura, Y. Kubota, H. Fujimoto, and K. Okamoto, J.C.S.Perkin II, 1981, 670.
2)
Horita,T. Otsubo, Y. a)J.G.O'Connor and P.M. Keehn, J.Am. Chem.soc., %,8446(1976);b)H. Sakata,and S.Misumi, Tetrahedron Lett., 1976, 3899;c) J. G. O'Connorand P.M.Keehn, ibid.,= e) H. Horita,T.Otsubo, and 3711; d)T. Nakazawaand I. Murata, J.Am. Chem. sot., 2,1996(1977); f)D. N. Butler and I. Gupta,cah. J. Chem., 56,80 (1978); g) K. S. Misumi, Chem. L&t., 1978,807; Komatsu, N.Abe, K. Takahashi, and K. Okamoto,J. Orq.Chem.,s, 2712 (1979);v K. Komatsu, K. Nakazawa,N. Abe,K. Kubo,and I. Takahashi, and K. Okamoto,retrahedron Lett., =,4747;i)T. !-%.Wata,ibid., m,4995;j) K. Yamamura,K. Nakatsu, K. Nakao,T. Nakazawa,and I. Murats, ibid., =,4999;k)T.Nakazawa,Y.Niimoto,K.Kubo, andI. Murata,nngew. Chem.,z, 566 (1980).
dication (Ref. 2c) nor that to 3) Neither an attempt to isolate [2.2](1,4)tropylioparacyclophane isolate 1,8-ditropylionaphthalene dication was successful due to rapid decomposition: K. Komatsu, N. Abe, and K. Okamoto, unpublished result. 4) T. Either and H. Berneth,
Tetrahedron
Lett.,
1973, 2039.
5) Also formed by complete neutralization of 1: IR v (KBr) 1800(m), 1125(m), 1100(m) trn-', UV h,, (MeCN) 230 nm (log E, 4.64), 247 (4.61), 314 (4.38), 328 (4.38), 350 (4.26); H NMR (220 MHz) 6 (CDC13) 8.26 (d, 2H, Naph-H-2), 7.91 (d, 2H, Naph-H-4), 7.87 (d, 4!, o-H), 7.60 (t, 2H, Naph-H-3), 7.46 (m, 6H, m,~-H), 7.17 (d, $1, O-H'), 6.97 (m, 6H, m,p-H A; 13C NMR 6 (CDC13) 144.1-124.2 (14 peaks, Ar-C), 119.2 (Kf ), 117.‘9 (qNaph), 65.8 (;,a); Anal. Calcd for C40H260:C, 91.92; H, 5.01%. Found:C, 91.52;H, 5.07%. 6) This method is similar to the one used for the synthesis of 5 (Ref. 4). The use of phenylchlorodiazirine as the carbene generator was found unsuitable becauseofthe instability of the first formed mono-carbene-adductunder the reaction conditions leading to a complexmixture of byproducts. 7) A comparable amount of upfield shift (A6 0.53)is observed for the facing phenyl protons in 1,8diphenylnaphthalene: H. 0. House, R. W. Magin, and.H. W.Thompson, J. org. Chem., Z&2403 (1963). 8) For example, see T. Kaneda, T. Otsubo, H. Horita, 1015 (1980), for the case of [n.n]paracyclophanes. 9) K. Komatsu, K. Masumoto, and K. Okamoto, Abstracts Aromatic Compounds (Sendai), p.23 (1976). 10) Lit. mp 312-314":
K. Rasheed,
Tetrahedron,
21,
and S. Misumi,~ull.
Chem.soc.Jpn.,
for the 9th Symposium
3,
on Nonbenzenoid
2957 (1966).
L&t., 1974, 11) For example, I. J. Landheer, W. H. de Wolf, and F. Brickelhaupt, Tetrahedron 2813, ibid., __ 1975, 349; J. H. Davis, K. J. Shea, and R. G. Bergman, Angew. Chem., 88, 254 (1976), and the references cited therein.
(Received in Japan 14 September 1981)