Deamination of 1-alkyl-9-aminomethyltriptycenes. Participation of a neighboring 1-alkyl substituent

Article abstract of DOI:10.1246/bcsj.79.1585

Deamination reactions of 1-alkyl-9-aminomethyltriptycenes (alkyl = Me, Et, i-Pr, and t-Bu) and 9-(1-aminoethyl)-1-methyltriptycene were performed in CHCl₃ and in AcOH, and product distributions were studied. The results suggest that the loss of

Full text of DOI:10.1246/bcsj.79.1585

ꢀ
2006 The Chemical Society of Japan
Bull. Chem. Soc. Jpn. Vol. 79, No. 10, 1585–1600 (2006) 1585
Deamination of 1-Alkyl-9-aminomethyltriptycenes.
Participation of a Neighboring 1-Alkyl Substituent
ꢀ
Gaku Yamamoto, Ai Koseki, Jun Sugita, Hisashi Mochida, and Mao Minoura
Department of Chemistry, School of Science, Kitasato University, 1-15-1 Kitasato, Sagamihara, Kanagawa 228-8555
Received May 8, 2006; E-mail: gyama@kitasato-u.ac.jp
Deamination reactions of 1-alkyl-9-aminomethyltriptycenes (alkyl = Me, Et, i-Pr, and t-Bu) and 9-(1-aminoethyl)-
-methyltriptycene were performed in CHCl3 and in AcOH, and product distributions were studied. The results suggest
1
that the loss of N2 from a primary alkanediazonium ion predominantly takes place concomitantly with participation of a
C–H bond of the neighboring 1-alkyl group to form a nonclassical cationic species with a three-center two-electron
bonding, while the loss of N2 from a secondary alkanediazonium ion occurs spontaneously to form a secondary carbo-
ꢁ
cation. Solvent effects (CHCl3 vs AcOH) are explained in terms of lower nucleophilicity/basicity of the AcO in AcOH
than in CHCl3 due to solvation.
Deamination reactions of aliphatic primary amines via di-
azotization of the amino group have attracted much attention
identifiable product in 31% yield.3
In 1987, we reported the diazotization of 9-aminomethyl-
1,4-dimethyltriptycene (3) with nitrous acid in AcOH, which
gave the cyclic hydrocarbon 4 (46%), the acetate 5 (34%),
and the chloride 6 (8%) together with small amounts of skel-
because they are said to generate poorly solvated (so-called
1
‘‘hot’’) carbocations. Reaction paths for the formation of cat-
ionic species from diazonium ions depend on the structure of
the substrate and the solvent used. It is highly intriguing to
know whether N2 is eliminated from the diazonium ion in an
SN1 fashion or in an SN2 fashion, and how the neighboring
groups participate in the loss of N2.
4
etally rearranged homotriptycene derivatives (Chart 2). We
postulated that the C–H bond of the 1-methyl group partici-
pates in the decomposition of the predominant ap-rotamer 7
of the diazonium ion from the rear of the leaving N2 in an
SN2-like fashion to afford a pentacoordinate carbocationic spe-
cies, 8, with a three-center two-electron bond, which either
gives 4 upon loss of a proton or migrates to the benzylic cation
9, the latter affording 5 and 6 upon addition of nucleophiles.
Alternatively and less likely, the diazonium ion 7 could afford
In 1970, Cristol and Pennelle reported that the reaction
of 9-aminomethyltriptycene (1: X ¼ NH2) with nitrous acid
(NaNO2/HCl) in AcOH gave skeletally rearranged homotri-
ptycene derivatives 2 (Y ¼ OH) and 2 (Y ¼ OAc) in yields of
2 and 56%, respectively, while the reaction of 1 (X ¼ NH2)
with nitrosyl chloride in CH2Cl2 gave the rearranged chloride
4
CH3 CH NH2
1
2
H C CH2
XCH2 CH3
2
(Y ¼ Cl) and the unrearranged chloride 1 (X ¼ Cl), in 66
2
2
and 12%, respectively (Chart 1). Although the authors made
no conclusive discussion, it is certain that the high ability of
N2 as a leaving group is responsible for these reactions. These
results are in contrast with the fact that the halides and the ace-
tate with the structure 1 resist solvolysis. 9-Chloromethyltri-
ptycene (1: X ¼ Cl) was recovered unchanged after treatment
9
CH3
CH3
CH3
3
C
4
5
6
: X = OAc
: X = Cl
ꢂ
with AgOAc in AcOH at 210 C for 24 h, and 9-acetoxymeth-
H
H
H
H
H
N2
H
H
H
H
yltriptycene (1: X ¼ OAc) was recovered unchanged after
CH3
H C
C
C
3
C
boiling for 2 h in 1 M HClO4 (1 M = 1 mol dm ) in AcOH.2
ꢁ
1
Heating 9-bromomethyltriptycene (1: X ¼ Br) in m-cresol
ꢂ
around 360 C gave 1-methyltriptycene (1: X ¼ H) as the sole
CH3
CH3
CH3
7
8
9
X
H C
2
H
H
H C
C
3
9
Y
CH3
1
2
10
Chart 1.
Chart 2.
Published on the web October 10, 2006; doi:10.1246/bcsj.79.1585

1
586 Bull. Chem. Soc. Jpn. Vol. 79, No. 10 (2006)
Deamination of 9-Aminomethyltriptycenes
the primary carbocation 10 in an SN1-like fashion, and then the
-methyl group could interact with the cation center of 10 to
give 8.
9-(1-aminoethyl)-1-methyltriptycene (15), an amine with a
secondary alkyl group.
1
þ
Results and Discussion
The protonated ethane species C2H7 has been extensively
5
studied both experimentally and theoretically. The bridged
structure similar to 8 has been shown to exist in an energy
Synthesis of the Substrates. At the outset, two synthet-
ic routes to the amino compounds 11–15 were considered
(Scheme 1). One route makes use of the directed lithiation of
a suitable 9-substituted triptycene followed by alkylation to
give 1-alkyl-substituted triptycenes, which are then converted
to 9-aminomethyl compounds by functional transformations
of the 9-substituent (Route A). The other route uses the reaction
of a 3-alkyl-substituted benzyne with a 9-substituted anthra-
cene to afford a 1-alkyl-substituted triptycene together with
the undesired regioisomer. The 1-alkyl compound is then sep-
arated and converted to a 9-aminomethyl compound by suitable
functional transformations of the 9-substituent (Route B).
As the starting material for Route A, 9-methoxymethyltrip-
þ
minimum as one of the possible isomers of C2H7 .
In order to have a deeper insight into this intriguing reac-
tion, we systematically studied the diazotization reactions of
9
-aminomethyltriptycene derivatives with a variety of 1-sub-
stituents under various reaction conditions. In this article, the
results of the deamination reactions of four 1-alkyl-9-amino-
methyltriptycenes 11–14 as well as the 1-trideuteriomethyl
compound 11a (Chart 3) with isopentyl nitrite in CHCl3 and
AcOH, and the mechanisms are discussed mainly based on
6
the product distributions. Also included are the results for
7
tycene was chosen, and the 1-methyl compounds 11 and 11a
were synthesized by this route (Scheme 2).
R
R'
R'
H
NH2
11
CH3
1a CD3
H
H
H
H
H
CH3
R
C
9-Methoxymethyltriptycene (17), prepared from 9-methoxy-
methylanthracene (16), was reacted with butyllithium to afford
1
1
1
1
1
1
2
3
4
5
CH CH3
CH(CH3)2
C(CH3)3
CH3
2
7
9
selectively the peri-lithiated intermediate, which was treated
with methyl iodide in the presence of a nickel(II) catalyst to
afford the 1-methyl compound 18 in 49% yield. Treatment of
4
10
18 with boron tribromide afforded the expected alcohol 19
with the cleavage of the CH3–O bond. The alcohol 19 was oxi-
Chart 3.
Route A
R1
Li R1
R
R1
BuLi
RX
Ni(II)
Route B
R2
R
R2
R R'CHNH2
R
1
1–15
Scheme 1.
CH OCH
CH2OCH3
R
CH2OCH3
2
3
1) BuLi
BBr3
2
) RI / NiII
16
17
18: R = CH3
8a: R = CD3
1
R
CH OH
R
CHO
R
CH=NOH
2
PCC
NH2OH
LiAlH4
11, 11a
1
1
9: R = CH3
9a: R = CD3
20: R = CH3
20a: R = CD3
21: R = CH3
21a: R = CD3
Scheme 2.

G. Yamamoto et al.
Bull. Chem. Soc. Jpn. Vol. 79, No. 10 (2006) 1587
R
R
R
R
H
N
H
O
N
NH2
NH2
O
H
NOH
COOH
O
2
2
2
2b: R = CH CH
2 3
2c: R = CH(CH3)2
2d: R = C(CH3)3
R = CH CH , CH(CH ) , C(CH )
R
2
3
3 2
3 3
N2
CO2
∆
R
R
1
CN
R
CN
1
9
9
+
1
0
1
0
CN
2
3
2
2
2
2
4: R = CH3
5: R = CH CH
6: R = CH(CH3)2
7: R = C(CH3)3
24a: R = CH3
25a: R = CH CH
26a: R = CH(CH3)2
27a: R = C(CH3)3
2
3
2
3
Scheme 3.
dized with pyridinium chlorochromate (PCC) to afford the cor-
responding aldehyde 20. Reaction of 20 with hydroxylamine
gave the corresponding oxime 21, which upon reduction with
LiAlH4 afforded the amine 11. The 1-trideuteriomethyl com-
pound 11a was synthesized in the same way.
In preliminary experiments, we found that an ethyl group
could be introduced in the peri-position in a similar manner,
but several attempts to introduce an isopropyl or an isopropen-
yl group failed presumably because of steric hindrance.
In the meantime, we explored the synthesis by way of Route
B in Scheme 1, and found that 9-cyanoanthracene (23) reacted
with benzyne to afford 9-cyanotriptycene, though 23 had been
8
reported not to react with benzyne. Since 9-cyanotriptycene
Fig. 1. ORTEP drawing of compound 26 with 50% proba-
bility thermal ellipsoids.
was expected to afford 9-aminomethyltriptycene in one step,
compound 23 was chosen as the starting anthracene. The 3-
alkylanthranilic acids 22b–22d, the precursors for the 3-alkyl-
benzynes, were synthesized from the corresponding 2-alkyl-
anilines, by way of the respective N-phenyl-2-hydroxyimino-
acetamides and isatins, as shown in Scheme 3, while 3-meth-
ylanthranilic acid (22a) was commercially available. Thermal
decomposition of 6-alkylbenzenediazonium-2-carboxylates,
prepared from the corresponding anthranilic acids and isopen-
tyl nitrite, in the presence of 23 afforded 1-alkyl-9-cyanotripty-
cene 24–27 together with the regioisomeric 1-alkyl-10-cyano-
triptycenes 24a–27a.
the plane of the aromatic ring, and further that, when two ortho
positions are substituted, the ꢁ-hydrogen tends to point to the
bulkier substituent. The conformation of the isopropyl group
in 26 conforms to the general findings.
9
The formation ratio of the regioisomers, as detected by the
NMR integration of the crude reaction mixture, was 37:63 for
24:24a, 45:55 for 25:25a, 50:50 for 26:26a, and 60:40 for
27:27a. The bulkier the alkyl group, the larger the formation
ratio of the apparently more crowded 1-alkyl-9-cyanotripty-
cene. This type of regioselectivity, that the more crowded
regioisomer is easily formed, has often been reported in other
Diels–Alder reactions,10 and has been explained in terms of the
transition state where two less hindered sites in the diene and
the dienophile become closer together.
The nitriles 24–26 were sufficiently reduced to the corre-
sponding amines 11–13 with LiAlH4 (Scheme 4), but the
nitrile 27 with a t-butyl group was not reduced probably due
to steric hindrance. Treatment of the methyl nitrile 24 with
methyllithium gave the imine 28, which was reduced with
LiAlH4 to the 9-(1-aminoethyl) compound 15.
1
Isomer assignments were made from the H NMR chemical
shifts of the bridgehead protons: the 10-H signal of the 9-cyano
compounds 24–27 appeared in a narrow range (ꢀ 5.38–5.41),
while the 9-H signal of the 10-cyano compounds 24a–27a
appeared at a lower field (ꢀ 5.67–6.25), which significantly
depended on the bulkiness of the alkyl group presumably
reflecting the steric compression of the alkyl group.
The assignments were further confirmed by the X-ray struc-
tural analysis of compound 26 (Fig. 1). Noteworthy in the mo-
lecular structure of 26 is the conformation of the 1-isopropyl
group: the ꢁ-hydrogen points toward the cyano group. It has
been shown that an isopropyl group bonded to an aromatic ring
prefers a conformation in which the ꢁ-hydrogen is located in
The t-butyl amine 14, which could not be obtained by
reduction of the nitrile 27, was therefore synthesized by way
of the phthalimide 30, which was synthesized by the addition

1
588 Bull. Chem. Soc. Jpn. Vol. 79, No. 10 (2006)
Deamination of 9-Aminomethyltriptycenes
R
CN
2
4
CH Li
3
CH3 C(CH )=NH
3
2
2
2
4: R = CH3
5: R = CH CH
2
3
6: R = CH(CH3)2
LiAlH4
28
R
CH NH
LiAlH4
Fig. 2. ORTEP drawing of compound 30 with 50% prob-
ability thermal ellipsoids.
2
2
CH3 CH(CH )NH2
3
R
R
R
H
H
H N
H
H
NH2
2
1
1
1
1: R = CH3
2: R = CH CH
2
3
15
NH2
H
H
3: R = CH(CH3)2
ap
+sc
−sc
Scheme 4.
Scheme 6.
t-Bu
t-Bu
1
4
NH2
N2
COOH
CO2
NH NH2
2
22d
∆
O
O
O
N
t-Bu
N
O
N
O
t-Bu
O
+
t-Bu
29
30
Scheme 5.
30a
of 3-t-butylbenzyne to 9-phthalimidomethylanthracene (29) as
shown in Scheme 5. In this case, the formation ratio of 30 and
its regioisomer 30a was ca. 2:3. The structure of 30 was deter-
mined by H NMR spectra: The bridgehead proton appeared at
ꢀ 5.36 and 6.25 for 30 and 30a, respectively. X-ray crystallog-
raphy confirmed the assignment (Fig. 2). Hydrazinolysis of 30
the methylene signal remained a sharp singlet throughout the
ꢂ
temperature range of 24 to ꢁ80 C, suggesting that the rotamer
equilibrium is almost one-sided to the ap isomer.
1
Therefore, it is reasonable to assume that the conformational
equilibrium is far shifted toward the ap isomer for compounds
11–14 at room temperature, at which the deamination reactions
were performed.
As for 1-(1-aminoethyl)-9-methyltriptycene (15), rotation
about the bridgehead-to-substituent bond was slow on the
NMR timescale at room temperature and two rotamers were
observed in an equilibrium ratio of 36:64 in CDCl3. Three
rotamers are assumed for 15 as shown in Scheme 7, but the
gave the desired amine 14.
1
In H NMR spectra of the amines 11–13 at room tempera-
ture, the signals were broad due to rotation of the aminomethyl
ꢂ
group on the NMR timescale. At ꢁ44 C, the rotation was suf-
ficiently slow and two sets of signals corresponding to two dis-
tinguishable rotational isomers, ap and ꢃsc (þsc and ꢁsc are
1
1
ꢀ
ꢀ
NMR-equivalent), were observed for the 1-methyl (11) and
R -ðþscÞ rotamer is probably energetically unfavorable due
ꢀ
ꢀ
1
9
-ethyl (12) compounds (Scheme 6). The isomer ratio was
5:5 for 11 and 96:4 for 12. The major isomer was assigned
to steric reasons and thus absent. The R -ðꢁscÞ rotamer was
assigned to the major isomer because the amino group is less
bulkier than the methyl group. NOE experiments supported
this deduction; two methyl groups were close to each other
in the minor isomer, but remote in the major.
to ap because the methylene protons gave a singlet, while the
minor to ꢃsc because the methylene protons gave an AB-type
quartet. In compound 13 with a 1-isopropyl group, the methyl-
ꢂ
ene protons gave a sharp singlet at ꢁ44 C, indicating that the
Deamination Reactions. Reactions were run in CHCl3 and
in AcOH according to the procedures given in the Experimen-
tal section, and the product ratio was determined by integration
fraction of the minor ꢃsc isomer was too small to be detected
at this temperature. In the amine 14 which has a t-butyl group,

G. Yamamoto et al.
Bull. Chem. Soc. Jpn. Vol. 79, No. 10 (2006) 1589
or a neighboring group from the backside of the leaving N2
in an SN2 fashion. Since no direct substitution products of
the amino group in 11 were observed, an SN2 reaction of an
outer nucleophile was eliminated. As a neighboring group, a
benzene ring of the triptycene skeleton would be considered,
as in the case of 1 (X ¼ NH2), which would give a homotripty-
cene skeleton. Formation of the homotriptycene 33 was actual-
ly observed but only in a small amount: Rearrangement of the
Me
Me
Me
H
H C
H
H
NH2
H N
CH3
3
2
NH2
ap
CH3
R*-(−sc)*
R*-(+sc)*
Scheme 7.
0
backside benzene ring in ap-11 to give a tertiary carbocation
ꢁ
1
of the H NMR signals of the crude reaction mixture. Each
reaction product was separated by GPC, isolated, and charac-
terized mainly by H NMR spectroscopy.
followed by reaction with AcO would afford 33. Another
0
homotriptycene 34 would be formed from ꢃsc-11 ; however,
1
it was not detected.
Deamination of 9-aminomethyl-1-methyltriptycene (11)
in CHCl3 afforded a cyclization product, 1,2,6,10b-tetrahy-
dro-6,10b-o-benzenoaceanthrylene (31), together with small
amounts of a rearranged acetate, 1-acetoxymethyl-9-methyl-
triptycene (32) and a homotriptycene, 10-acetoxy-10,11-di-
hydro-1-methyl-5,10-o-benzeno-5H-dibenzo[a,d]cycloheptene
The most abundant product in both CHCl3 and AcOH was
1,2,6,10b-tetrahydro-6,10b-o-benzenoaceanthrylene (31), and
its formation is explained as follows. Nucleophilic participa-
tion of the ꢂ-electrons of a C–H bond of the 1-methyl group
0
from the backside of the leaving N2 in ap-11 would afford
a ‘‘protonated ethane’’ type intermediate species 35, as was
4
(
33) in a ratio of 95:3:2 (Scheme 8). In AcOH, the proportion
postulated previously (see 8). Cleavage of the three-mem-
of 32 significantly increased at the expense of 31 together with
a small increase in 33.
bered ring in 35 would result in the elimination of the bridging
proton and formation of 31, while another way of the ring
cleavage gave a benzylic carbocation 36, which afforded the
Structure determinations and NMR spectral assignments of
these products were made as follows. Compound 31 showed,
together with the signals due to the triptycene skeleton,
ꢁ
rearranged acetate 32 upon reaction with AcO . The third
way of cleavage to give the primary carbocation 37 would be
far less favorable, and no products from 37 were found.
In CHCl3, the cationic species 35 forms a tight ion-pair, and
0
0
AA BB multiplets at ꢀ 3.25 and 3.35, to which 1-H and 2-H,
respectively, were assigned based on NOE (10-H ! 1-H,
ꢁ
3
-H ! 2-H). 1-C and 2-C were shown to appear at ꢀ 22.8
the counter anion AcO easily abstracts the bridging proton
from 35. Thus, only a small amount of 35 can survive long
enough to give 36. In AcOH, on the other hand, outer nucleo-
and 33.2, respectively, based on CH-COSY. For compound
2, NOE unambiguously showed that this compound was 1-
acetoxymethyl-9-methyltriptycene and not 9-acetoxymethyl-
-methyltriptycene; irradiation of the methyl signal at ꢀ 2.65
3
ꢁ
philes such as AcO are well solvated and less reactive than in
1
CHCl3, which renders the abstraction of the bridging proton
less efficient and instead allows rearrangement to the benzylic
cation 36, resulting in the increase in the formation ratio of 32
in AcOH.
enhanced the intensity of the two-proton multiplet signal at
the lowest-field of the aromatic region (ꢀ 7.39), which were
assigned to 8/13-H. For compound 33, the one-proton singlet
at ꢀ 4.90 was characteristic of the bridgehead proton of the
homotriptycene skeleton, and NOE enhancement of the aro-
matic methyl signal at ꢀ 2.04 upon irradiation of the methylene
signal at ꢀ 3.12 clearly showed that the methyl group was
attached to 1-C and not to 9-C.
There is no experimental evidence for the nonclassical cat-
ionic species 35; however, it is proposed as a logical inter-
mediate which reasonably explain the observed results.
Deamination of 9-aminomethyl-1-[D3]methyltriptycene (11a)
gave the results shown in Scheme 10; products with the homo-
triptycene skeleton were not detected. Structures of the prod-
ucts and the deuterium distribution were determined by MS
We propose the following mechanistic scheme to ex-
plain the product distributions and the solvent dependence
1
(Scheme 9). As described above, the rotamer equilibrium in
the amine 11 is shifted to the ap isomer, and thus the diazoni-
and NMR. For 31a, it was unambiguously shown by both H
1
3
1
and C NMR that no deuterium was incorporated at C , while
2
0
um ion 11 formed from 11 will also exists mainly as the ap
0
two deuterium atoms were at C . The 9-methyl group of 32a
rotamer. SN1-type elimination of N2 from 11 should give a
primary carbocation. However, this process should be energet-
contained one deuterium atom, while the methylene group
contained two deuterium atoms. These results are consistent
with the intermediacy of 35, in which no deuterium scrambling
occurs. The increase in the ratio of 32a/31a (35/65) relative to
ically very unfavorable. N2 elimination requires nucleophilic
ꢁ
assistance by an outer nucleophile (AcO , AcOH, or H2O)
NH2
2
1
AcO
OAc
1
3
1
1
1
1
3
10
2
9
1
0
8
9
6
11
31
32
33
Solvent
CHCl3
AcOH
95%
70
3
26
2
4
Scheme 8.

1
590 Bull. Chem. Soc. Jpn. Vol. 79, No. 10 (2006)
Deamination of 9-Aminomethyltriptycenes
H
H
H
NH2
NH2
H
C
C
ap-11
±sc-11
H
H
H
C
H
H
H
N2
N2
C
H
C
AcO
OAc
ap-11'
±sc-11'
AcO
H
H
AcO
C
H
H
H
H
H
C
C
33
37
34
−
H
H
H
AcO
AcO
C
35
31
36
32
Scheme 9.
2
1
NH2
AcO
CD3
D C CH2
CD CH D
2
2
2
+
1
1a
31a
32a
Solvent
CHCl3
AcOH
97%
65
3
35
Scheme 10.
R
NH2
AcO
HO
R
1
1
2: R = H
3: R = CH3
38
39
40
41
42
R = H R = CH3
Solvent
CHCl3
AcOH
6%
−
61
> 99
3
−
30
−
> 99
> 99
Scheme 11.
that of 32/31 (26/70) found in AcOH may be due to isotope
effects; i.e., the bridging deuteron is less easily removed from
a small amount of the cyclization product 38, while in AcOH
the rearranged acetate 39 was detected as the sole product
(Scheme 11). Deamination of 9-aminomethyl-1-isopropyltrip-
tycene (13) afforded the rearranged alkene 42 as the sole
product both in CHCl3 and AcOH (Scheme 11). Structures
3
5a than the bridging proton is from 35.
Deamination of 9-aminomethyl-1-ethyltriptycene (12) in
CHCl3 mainly gave rearranged products 39–41 together with

G. Yamamoto et al.
Bull. Chem. Soc. Jpn. Vol. 79, No. 10 (2006) 1591
H
R
H
NH2
H C
3
CH C
1
1
2: R = H
3: R = CH3
−
H
3
8
AcO
H
HH H
R
R
H
N2
H C
R
3
H C
H
AcO
C
C
3
C
C
3
9
H O
2
4
4
4
3
R = H, CH3
−
H
HO
H
H
H
H
R
C
H
H
R
C
C
4
0
4
4
1: R = H
2: R = CH3
4
5
Scheme 12.
H
H
H
H
H
H
C
H3C
H3C
C
H C
3
H
H
NH2
N2
C
C
C
H C
2
H C
3
14
47
−
H
4
6
48
Scheme 13.
of these compounds were determined without difficulty by
1
ton from the methyl group is favored.
using H NMR.
It should be noted that no products were observed that might
be produced by way of the intermediate species 45, which
would form by the participation of the ꢃ-C–H bond of the
1-alkyl group. This is partly ascribed to the conformation of
the 1-alkyl group. The conformation in which the ꢁ-hydrogen
points toward the bridgehead substituent is most stable, and the
ꢃ-hydrogens are located too far to participate in N2 elimina-
tion.
Deamination of 9-aminomethyl-1-t-butyltriptycene (14) af-
forded a cyclized product, 3,3-dimethyl-2,3,7,11b-tetrahydro-
7,11b-o-benzeno-1H-benzo[d,e]anthracene (46) as the sole
product both in CHCl3 and AcOH (Scheme 13). The molecu-
lar structure of 46 was confirmed by X-ray crystallography
(Fig. 3).
Possible mechanistic pathways are shown in Scheme 12.
The three-center two-electron species 43 is again postulated
as an intermediate. The ꢂ-electrons of an ꢁ-C–H bond of
the 1-alkyl group act as a nucleophile and attack the ꢁ-carbon
of the diazonium ion in the ap rotamer to give 43. Deprotona-
tion of 43 (R ¼ H) gives 38, but this is not the predominant
path. The benzylic cation 44 (R ¼ H) is more stable than 36
in Scheme 9, and thus 43 rearranges to 44 more easily, which
gives the acetate 39 and the alcohol 40 upon reaction with out-
er nucleophiles, and the alkene 41 upon deprotonation. In the
deamination of the isopropyl compound 13, the benzylic cation
4
4 (R ¼ CH3) is even more stable, and the entire reaction pro-
ceeds via this species. The sole formation of alkene 42 by de-
protonation of 44 (R ¼ CH3) and the absence of substitution
products, such as an acetate, may be due to the steric reasons:
A C–H bond of the t-butyl group that is located in a proper
position assists in the elimination of N2 to form a cationic spe-
cies 47, which will upon deprotonation afford 46. If the reac-
tion followed a different cleavage pathway in 47, a tertiary
ꢁ
In 44 (R ¼ CH3), approach of AcO to the cationic center is
more hindered than in 44 (R ¼ H), and thus abstraction of pro-

1
592 Bull. Chem. Soc. Jpn. Vol. 79, No. 10 (2006)
Deamination of 9-Aminomethyltriptycenes
benzylic cation 48 would be formed by rearrangement of a
methyl group, which is often observed in a neophyl system.
This does not occur even in AcOH.
both in CHCl3 and in AcOH. The mixture of these two isomers
was easily separated from the other products, but the complete
mutual separation of the two by chromatography could not be
made. Fortunately, crystallization of the mixture from diethyl
ether–hexane afforded single crystals of 54. X-ray crystallo-
graphic analysis of 54 revealed that this compound is the
9,11-dimethyl isomer, and that two methyl groups are in the
The results for 14 may be compared with those in a pre-
¯
12
vious report by Oki et al. that deamination of the ꢃsc ro-
tamer of compound 49 in boiling benzene afforded the cycliza-
tion product 50 in 28% yield together many other products
ꢀ
ꢀ
ꢀ
(Scheme 14).
Deamination of 9-(1-aminoethyl)-1-methyltriptycene (15)
anti orientation, i.e. the configurations are 5R ; 10R ; 11R
1
13
(Fig. 4). H and C NMR data of pure 54 could be obtained,
while those of 53 were obtained for a sample of the homotri-
ptycene mixture and by subtracting the signals of 54. The
proximity of the two methyl groups in 53 was clearly shown
by NOE confirming that it is the 1,11-dimethyl isomer.
Plausible mechanistic pathways are shown in Scheme 16 for
15 with the (R)-configuration, though the racemic compound
was used in the deamination reactions. It is reasonable to as-
sume that secondary carbocations are formed from secondary
alkanediazonium ions by spontaneous loss of N2. Thus, rota-
gave products as shown in Scheme 15. Irrespective of the sol-
vent, no products in which the 1-methyl group participated
were detected. In CHCl3, 9-substituted 1-methyltriptycene de-
rivatives 51 and 52 were the predominant products together
with small amounts of homotriptycene derivatives 53 and 54.
In AcOH, the amounts of the homotriptycenes 53 and 54 in-
creased at the expense of the triptycenes 51 and 52.
Structures of 51 and 52 were unambiguously determined by
NMR spectroscopy including the NOE experiments. The ace-
tate 52 existed as two rotamers in an equilibrium ratio of 72:28
0
0
meric diazonium ions ap-15 and R-ðꢁscÞ-15 afford rotameric
carbocations 55 and 55a, respectively, which then give rise to
the alkene 51 and the acetate 52, upon reaction with the outer
ꢀ
ꢀ
and the R -ðꢁscÞ conformation was assigned to the major
isomer with the similar reasoning as in the case of 15. The
homotriptycenes 53 and 54 were formed in a ratio of ca. 1:2
ꢁ
nucleophile/base AcO , or rearrange to the homotriptycene
cations 56 and 57. The larger formation ratio of the homotri-
ptycenes 53 and 54 in AcOH (15%) than in CHCl3 (2%) is as-
ꢁ
cribed to the lower nucleophilicity/basicity of AcO in AcOH
than in CHCl3, as discussed before in the case of the deamina-
tion of the amine 11. The skeletal rearrangement of 55 will
form the tertiary cation 56, which results in the acetate 53,
while that of 55a will form 57 and finally 54. Absence of
the diastereomeric homotriptycene 58 in the products indicates
that rotameric carbocation 55b is not formed. There are two
Fig. 3. ORTEP drawing of compound 46 with 50% prob-
ability thermal ellipsoids.
NH2
49
50
Fig. 4. ORTEP drawing of compound 54 with 50% prob-
ability thermal ellipsoids.
Scheme 14.
NH2
OAc
OAc
OAc 9
10
11
1
1
1
5
1
5
51
52
53
0.7
5
54
1.3
10
Solvent
CHCl3
AcOH
85%
77
13
8
Scheme 15.

G. Yamamoto et al.
Bull. Chem. Soc. Jpn. Vol. 79, No. 10 (2006) 1593
H
H
NH2
CH3
H C
H C
3
3
NH2
C
C
H C
3
ap-15
R-(−sc)-15
H
H
H C
H C
N2
CH3
3
N2
3
C
C
H C
3
CH3
CH3
H
CH3
H
H C
3
ap-15'
R-(−sc)-15'
− N2
−
N2
5
6
57
HCH3
C
H CH3
AcO
CH3
AcO
H C
C
3
?
CH3
H C
3
H
H
OAc
OAc
CH3
H C
3
5
5
55a
5
3
54
H CH3
C
OAc
H C
H
3
OAc
CH3
CH3
+
5
1
52
Scheme 16.
55b
58
possible reasons: (1) the skeletal rearrangement takes place
faster than the rotation of the bridgehead-to-cationic carbon
bond, and (2) the cation 55b is much less stable than 55 or
Experimental
General. Melting points are not corrected. Mass spectra were
obtained on a Hitachi M-2500 spectrometer in an EI mode. Prep-
arative gel permeation chromatography (GPC) was performed on
an LC-908 or an LC-918 apparatus of Japan Analytical Instru-
ments Co., Ltd. using a series of JAIGEL 1H and 2H columns
5
5a probably due to the steric repulsion between the methyl
groups. No definite conclusion on this point can be drawn at
the present stage.
and CHCl as the eluent. H and 13C NMR spectra were obtained
1
Conclusion
3
on a Bruker ARX-300 spectrometer operating at 300.1 MHz for
1
The results presented above indicate that elimination of N2
from primary alkanediazonium ions predominantly occurs
with concomitant formation of a nonclassical cationic species
with a three-center two-electron bonding, through participation
of the C–H bond from a neighboring 1-alkyl group, which then
gives a cyclized product by a proton loss, or 1-acetoxymethyl
or 1-vinyl derivatives of 9-methyltriptycene by way of a ben-
zylic cation. On the other hand, N2 elimination from a secon-
dary alkanediazonium ion mostly takes place spontaneously to
form a classical secondary carbocation, which then affords un-
rearranged 9-acetoxymethyl- or 9-vinyltriptycene derivatives,
or skeletally rearranged homotriptycene derivatives. Solvent
effects (CHCl3 vs AcOH) are explained in terms of the lower
13
H and 75.4 MHz for C, respectively, or on a Bruker AVANCE
1
II 600 spectrometer operating at 600.1 MHz for H and 150.9 MHz
for 13C, respectively. Chemical shifts were referenced with inter-
1
nal tetramethylsilane (ꢀH 0.0) or CDCl3 (ꢀC 77.0). Data of H and
C spectra given below are obtained at 22–24 C unless otherwise
13
ꢂ
stated. Letters p, s, t, and q given with the 13C chemical shifts
denote primary, secondary, tertiary, and quaternary, respectively.
In variable-temperature experiments, temperatures were calibrated
using methanol13 or ethylene glycol14 and are reliable to ꢃ1 ꢂC.
9
-Methoxymethylanthracene (16). To a solution of 9-hy-
droxymethylanthracene (5.0 g, 24 mmol) in tetrahydrofuran (100
mL) was added a solution of butyllithium in hexane (1.6 M, 15
ꢂ
ꢂ
mL, 24 mmol) at 0 C and the mixture was stirred for 1 h at 0 C.
To this solution was added dropwise methyl iodide (2.24 mL, 36
mmol), and the mixture was allowed to warm up to room temper-
ꢁ
nucleophilicity/basicity of AcO in AcOH than in CHCl3 due
to solvation.

1
594 Bull. Chem. Soc. Jpn. Vol. 79, No. 10 (2006)
Deamination of 9-Aminomethyltriptycenes
ature and stirred overnight. The mixture was extracted with dieth-
yl ether, and the extracts were washed with water and dried over
MgSO4, and the solvent was evaporated. Recrystallization from
0.97 g (3.29 mmol, 98%) of 20. Recrystallization from CH2Cl2–
ꢂ
hexane gave a pure sample of 20, mp 183–185 C. Anal. Found:
C, 88.88; H, 5.59%. Calcd for C22H16O: C, 89.16; H, 5.44%.
ꢂ
1
CH2Cl2–hexane gave 4.44 g (20 mmol, 82%) of 16, mp 89–90 C
H NMR (CDCl3) ꢀ 2.464 (3H, s), 5.336 (1H, s), 6.807 (1H, dd,
ꢂ
1
(
lit.15 90–91 C). H NMR (CDCl3) ꢀ 3.542 (3H, s), 5.431 (2H, s),
J ¼ 7:7, 0.6 Hz), 6.944 (1H, t, J ¼ 7:5 Hz), 7.02–7.05 (4H, m),
7
.24–7.57 (4H, m), 8.008 (2H, dd, J ¼ 8:4, 0.6 Hz), 8.379 (2H, dd,
7.286 (1H, dm, J ¼ 7:2 Hz), 7.397 (2H, m), 7.916 (2H, m), 11.319
13
13
J ¼ 8:4, 0.6 Hz), 8.458 (1H, s). C NMR (CDCl3) ꢀ 58.33 (1C,
(1H, s). C NMR (CDCl3) ꢀ 23.12 (1C, p), 54.93 (1C, t), 61.90
p), 66.57 (1C, s), 124.22 (2C, t), 124.92 (2C, t), 126.18 (2C, t),
(1C, q), 122.28 (1C, t), 123.23 (2C, t), 123.74 (2C, t), 125.14
(2C, t), 125.73 (2C, t), 126.02 (1C, t), 129.11 (1C, t), 132.03
(1C, q), 141.24 (1C, q), 142.50 (2C, q), 146.09 (2C, q), 146.41
(1C, q), 201.43 (1C, t).
1
1
28.36 (1C, t), 128.62 (1C, q), 129.00 (2C, t), 130.98 (2C, q),
31.40 (2C, q).
9
-Methoxymethyltriptycene (17). A slurry of benzenediazo-
1
6
nium-2-carboxylate, prepared from anthranilic acid (13.5 g,
8 mmol), in CHCl3 (100 mL) was added in small portions to a
boiling solution of 9-methoxymethylanthracene (16) (5.70 g,
.6 mmol) in CHCl3 (100 mL) during the course of 2 h, and the
1-Methyltriptycene-9-carbaldehyde Oxime (21). A mixture
of 20 (0.75 g, 2.53 mmol) and hydroxylamine hydrochloride
(1.00 g, 14.6 mmol) in pyridine (35 mL) was heated under reflux
for 6 h. After neutralization of the mixture with dil HCl, the mix-
ture was extracted with benzene. The extracts were washed with
water and dried over MgSO4, and the solvent was evaporated.
Recrystallization from CH2Cl2–hexane gave 0.71 g (2.18 mmol,
9
5
mixture was heated under reflux for 2 h. After removal of the sol-
vent, the residue was subjected to column chromatography on alu-
mina with hexane–ethyl acetate (3:1) as the eluent affording 3.87 g
ꢂ
ꢂ
(
13.0 mmol, 51%) of 17, mp 185–187 C. Anal. Found: C, 88.50;
1
95%) of 21, mp 241–243 C. Anal. Found: C, 84.80; H, 5.61;
N, 4.37%. Calcd for C22H17NO: C, 84.86; H, 5.50; N, 4.50%.
H, 6.11%. Calcd for C22H18O: C, 88.56; H, 6.08%. H NMR
1
(
(
CDCl3) ꢀ 3.813 (3H, s), 4.942 (2H, s), 5.361 (1H, s), 6.93–7.04
6H, m), 7.32–7.48 (6H, m). C NMR (CDCl3) ꢀ 53.25 (1C, q),
H NMR (CDCl3) ꢀ 2.483 (3H, s), 5.338 (1H, s), 6.780 (1H,
1
3
dm, J ¼ 7:7 Hz), 6.905 (1H, t, J ¼ 7:5 Hz), 6.97–7.08 (4H, m),
7.262 (1H, dd, J ¼ 7:2, 0.8 Hz), 7.370 (2H, m), 7.64 (1H, br s,
OH), 7.860 (2H, m), 8.891 (1H, s). 13C NMR (CDCl3) ꢀ 23.67
(1C, p), 55.08 (1C, t), 55.23 (1C, q), 122.15 (1C, t), 123.45 (2C,
t), 123.97 (2C, t), 124.94 (2C, t), 125.47 (2C, t), 125.68 (1C, t),
129.76 (1C, t), 132.75 (1C, q), 142.52 (1C, q), 144.29 (2C, q),
145.92 (2C, q), 146.26 (1C, q), 153.39 (1C, t).
5
1
4.28 (1C, t), 59.51 (1C, p), 71.02 (1C, s), 122.31 (3C, t, br),
23.32 (3C, t), 124.99 (6C, t), 144.79 (3C, q), 146.50 (3C, q).
9-Methoxymethyl-1-methyltriptycene (18). A solution of
butyllithium in hexane (16 M, 5.4 mL, 9.0 mmol) was added to a
solution of 17 (0.90 g, 3.0 mmol) and tetramethylethylenediamine
ꢂ
(
the mixture was stirred for 5 h. To the mixture was added methyl
TMEDA) (1.4 mL, 9.0 mmol) in diethyl ether (5 mL) at 0 C, and
7
9-Aminomethyl-1-methyltriptycene (11). To a suspension of
LiAlH4 (70 mg, 2.0 mmol) in diethyl ether (10 mL) was added
dropwise a solution of the 1-methyl oxime 21 (100 mg, 0.32
mmol) in diethyl ether (20 mL), and the mixture was stirred for
5 h at ambient temperature. The mixture was quenched with ethyl
acetate and water and extracted with diethyl ether. The extracts
were washed with water and dried over MgSO4, and the solvent
was evaporated. The residue was recrystallized from CH2Cl2–hex-
iodide (1.0 mL, 16.0 mmol) and NiCl2(DPPP) [DPPP = 1,3-bis-
(
diphenylphosphino)propane] (100 mg), and the mixture was stir-
red for 15 h at ambient temperature. The mixture was partitioned
with diethyl ether and water, and the ether layer was washed with
water, dried over MgSO4 and evaporated. The residue was sub-
jected to preparative GPC to afford 0.460 g (1.47 mmol, 49%) of
1
of 18, mp 225–227 C. Anal. Found: C, 88.23; H, 6.60%. Calcd
8. Recrystallization from CH2Cl2–hexane gave a pure sample
ꢂ
ꢂ
ane to give 69 mg (0.23 mmol, 72%) of 11, mp 180–182 C. Anal.
Found: C, 88.66; H, 6.54; N, 4.69%. Calcd for C22H19N: C, 88.85;
1
for C23H20O: C, 88.43; H, 6.45%. H NMR (CDCl3) ꢀ 2.59 (3H,
br s), 3.753 (3H, s), 4.5–5.4 (2H, br), 5.287 (1H, s), 6.5–7.9 (11H,
1
H, 6.44; N, 4.71%. H NMR (CDCl3) ꢀ 1.679 (2H, br s, NH2),
2.566 (3H, br s), 4.679 (2H, br s), 5.288 (1H, s), 6.5–7.8 (11H,
br m).
1
ꢂ
br m). H NMR (CDCl3) at ꢁ29 C showed the presence of two
rotamers, ap and ꢃsc, in a ratio of 59:41; the ap isomer: ꢀ
ꢂ
2
7
4
.552 (3H, s), 3.790 (3H, s), 5.221 (2H, s), 5.354 (1H, s), 6.69–
.54 (11H, m); the ꢃsc isomer: ꢀ 2.669 (3H, s), 3.765 (3H, s),
.794 (1H, d, J ¼ 9:8 Hz), 5.096 (1H, d, J ¼ 9:8 Hz), 5.354 (1H,
In the NMR spectrum at ꢁ44 C, rotation about the Tp-
CH2NH2 bond is frozen and ca. 95% of 11 exist as the ap-
1
ꢂ
rotamer: H NMR (CDCl3, ꢁ44 C) ꢀ 2.014 (2H, br s), 2.569 (3H,
s), 4.695 (2H, s), 5.382 (1H, s), 6.703 (1H, dm, J ¼ 7:5 Hz), 6.818
(1H, t, J ¼ 7:5 Hz), 7.02–7.17 (4H, m), 7.201 (1H, dm, J ¼ 6:8
Hz), 7.488 (2H, m), 7.610 (2H, m). For the minor ꢃsc isomer,
s), 6.78–7.68 (11H, m).
9-Hydroxymethyl-1-methyltriptycene (19). To a solution of
1
8 (0.62 g, 2.0 mmol) in CH2Cl2 (20 mL) was added a 1.0 M solu-
ꢂ
tion of BBr3 (18 mL, 18 mmol) in CH2Cl2 and the mixture was
stirred for 1 h at ambient temperature. The mixture was partitioned
between water and CH2Cl2 and the organic layer was washed with
water and dried over MgSO4, and the solvent was evaporated. The
the following signals were detected at ꢁ44 C: ꢀ 2.79 (3H, s),
13
ꢂ
4.32 (1H, d, J ¼ 12 Hz). C NMR (CDCl3, ꢁ44 C) ꢀ 22.81 (1C,
p), 41.35 (1C, s), 54.75 (1C, t), 58.59 (1C, q), 121.95 (1C, t),
123.06 (2C, t), 123.85 (2C, t), 124.71 (1C, t), 124.74 (2C, t),
125.25 (2C, t), 129.67 (1C, t), 132.23 (1C, q), 143.31 (1C, q),
143.81 (2C, q), 146.25 (2C, q), 148.93 (1C, q).
residue was recrystallized from CH2Cl2–hexane to give 0.54 g
ꢂ
(
1.8 mmol, 90%) of 19, mp 174–175 C. Anal. Found: C, 88.46;
H, 6.13%. Calcd for C22H18O: C, 88.56; H, 6.08%. 1H NMR
9-Aminomethyl-1-[D3]methyltriptycene (11a): Compound
11a was synthesized in the same manner as 11, by reaction
of lithiated 17 with CD3I instead of CH3I and the subsequent
(
CDCl3) ꢀ 2.16 (1H, br), 2.47 (3H, br s), 5.313 (1H, s), 5.43
(
2H, br s), 6.6–7.9 (11H, br m).
ꢂ
1
1-Methyltriptycene-9-carbaldehyde (20). To a solution of
transformations as shown in Scheme 2. Mp 182–183 C. H NMR
(CDCl3) ꢀ 1.716 (2H, br s, NH2), 4.675 (2H, br s), 5.293 (1H, s),
6.5–7.8 (11H, br m). MS m=z 300 (M , 100%), 283 (70%).
1
9 (1.00 g, 3.35 mmol) in CH2Cl2 (40 mL) was added pyridinium
þ
chlorochromate (PCC) (2.25 g, 10 mmol) and the mixture was stir-
red at ambient temperature for 2 h. The mixture was extracted
with diethyl ether and the extracts were subjected to column chro-
matography on silica gel with CH2Cl2 as the eluent affording
General Procedure for the Preparation of N-(2-Alkylphen-
yl)-2-hydroxyiminoacetamides. To a solution of chloral hydrate
(36 g, 0.22 mol) and sodium sulfate decahydrate (500 g) in 1.5 L of

G. Yamamoto et al.
Bull. Chem. Soc. Jpn. Vol. 79, No. 10 (2006) 1595
ꢂ
water was added successively a solution of o-alkylaniline (0.18
mol) and concd HCl (17 mL) in water (200 mL) and a solution
of hydrazine hydrochloride (42 g, 0.60 mol) in water (100 mL)
and the mixture was heated until boiling during the course of
ic Acids. To a hot (ca. 80 C) solution of 7-alkylisatin (0.10 mol)
in 10% aqueous sodium hydroxide (80 mL) was added dropwise
23 mL of 30% hydrogen peroxide. After cooling to room temper-
ature, the solution was treated with activated carbon and neutral-
ized with hydrochloric acid. The precipitates were collected by fil-
tration and purified by sublimation under reduced pressure.
3-Ethylanthranilic Acid (22b): Compound 22b was obtained
1
h and heated under reflux for 2 min. Precipitated solids on stand-
ing overnight were collected by filtration, and were dissolved in aq
NaOH. The solution was treated with activated charcoal, and neu-
tralized with HCl. The precipitates were collected by filtration,
air-dried, and recrystallized from ethanol.
in 83% yield, mp 158–159 C (lit. 147–148 C). 1H NMR
(CDCl3) ꢀ 1.283 (3H, t, J ¼ 7:4 Hz), 2.577 (2H, q, J ¼ 7:3 Hz),
ca. 6.5 (3H, br), 6.664 (1H, t, J ¼ 7:5 Hz), 7.256 (1H, d, J ¼
ꢂ
17
ꢂ
N-(2-Ethylphenyl)-2-hydroxyiminoacetamide:
pound was obtained in 69% yield, mp 107–108 C (lit. 105–
This com-
17
ꢂ
13
6:6 Hz), 7.864 (1H, d, J ¼ 7:7 Hz). C NMR (CDCl3) ꢀ 12.39
ꢂ
1
1
06 C). H NMR (CDCl3) ꢀ 1.245 (3H, t, J ¼ 7:5 Hz), 2.633 (2H,
(1C, p), 23.67 (1C, s), 109.10 (1C, q), 115.90 (1C, t), 128.50
(1C, q), 129.95 (1C, t), 133.61 (1C, t), 149.22 (1C, q), 174.05
(1C, q).
q, J ¼ 7:5 Hz), 7.11–7.28 (3H, m), 7.617 (1H, s), 7.947 (1H, d,
1
3
J ¼ 8:1 Hz), 8.29 (1H, br), 8.53 (1H, br s). C NMR (CDCl3) ꢀ
3.89 (1C, p), 24.29 (1C, s), 122.88 (1C, t), 125.71 (1C, t), 126.82
1C, t), 128.72 (1C, t), 134.01 (1C, q), 134.67 (1C, q), 144.98 (1C,
1
(
3-Isopropylanthranilic Acid (22c):
Compound 22c was
ꢂ
19
ꢂ
1
obtained in 72% yield, mp 99–100 C (lit. 98–99 C). H NMR
(CDCl3) ꢀ 1.266 (6H, d, J ¼ 6:9 Hz), 2.873 (1H, sept, J ¼ 6:9
Hz), ca. 6.2 (3H, br), 6.685 (1H, t, J ¼ 7:8 Hz), 7.314 (1H, dd, J ¼
t), 160.13 (1C, q).
N-(2-Isopropylphenyl)-2-hydroxyiminoacetamide:
This
compound was obtained in 89% yield, mp 109–110 C (lit. 104–
ꢂ
18
13
7:5, 1.3 Hz), 7.873 (1H, dd, J ¼ 8:1, 1.6 Hz). C NMR (CDCl3)
ꢂ
1
1
08 C). H NMR (CDCl3) ꢀ 1.245 (6H, d, J ¼ 6:9 Hz), 3.028
ꢀ 22.02 (2C, p), 27.20 (1C, t), 109.24 (1C, q), 115.99 (1C, t),
129.82 (1C, t), 131.01 (1C, t), 133.02 (1C, q), 148.68 (1C, q),
174.02 (1C, q).
(1H, sept, J ¼ 6:9 Hz), 7.16–7.26 (2H, m), 7.303 (1H, m), 7.606
(
1H, s), 7.773 (1H, m), 8.33 (1H, br s), 9.32 (1H, br s). 13C NMR
(CDCl3) ꢀ 22.89 (2C, p), 28.11 (1C, t), 124.10 (1C, t), 125.80 (1C,
3-t-Butylanthranilic Acid (22d): Compound 22d was ob-
ꢂ
19
ꢂ
1
t), 126.37 (1C, t), 126.49 (1C, t), 132.91 (1C, q), 140.36 (1C, q),
1
tained in 75% yield, mp 185–187 C (lit. 190–192 C). H NMR
(CDCl3) ꢀ 1.444 (9H, s), ca. 6.1 (3H, br), 6.628 (1H, t, J ¼ 7:8
Hz), 7.412 (1H, dd, J ¼ 7:5, 1.5 Hz), 7.900 (1H, dd, J ¼ 8:1,
44.53 (1C, t), 160.82 (1C, q).
N-(2-t-Butylphenyl)-2-hydroxyiminoacetamide: This com-
ꢂ
18
13
pound was obtained in 47% yield, mp 156–157 C (lit. 151–
1.5 Hz). C NMR (CDCl3) ꢀ 29.62 (3C, p), 34.27 (1C, q),
ꢂ
1
1
1
1
52 C). H NMR (CDCl3) ꢀ 1.414 (9H, s), 7.166 (1H, td, J ¼ 7:8,
.5 Hz), 7.255 (1H, td, J ¼ 7:8, 1.5 Hz), 7.409 (1H, dd, J ¼ 7:9,
.5 Hz), 7.640 (1H, s), 7.791 (1H, dd, J ¼ 7:8, 1.5 Hz), 8.50 (1H,
109.86 (1C, q), 115.53 (1C, t), 130.53 (1C, t), 132.32 (1C, t),
133.87 (1C, q), 150.18 (1C, q), 174.16 (1C, q).
General Procedure for the Preparation of 1-Alkyl-9-cyano-
triptycenes (24–27). To a boiling solution of 9-cyanoanthracene
(23) (3.00 g, 14.8 mmol) in CHCl3 (30 mL) were added simultane-
ously a solution of 3-alkylanthranilic acid (40 mmol) in CHCl3
(70 mL) and a solution of isopentyl nitrite (12 mL, 89 mmol) in
CHCl3 (70 mL) over the course of 4 h, and the mixture was stirred
under reflux for 1 h. Column chromatography of the mixture on
silica gel with hexane–benzene (5:1) as the eluent afforded a mix-
ture of 1-alkyl-9-cyanotriptycene and its regioisomer, 1-alkyl-10-
cyanotriptycene. GPC of the mixture afforded both isomers sepa-
rately after at least 20 recycles. Recrystallization from chloro-
form–hexane gave pure samples.
13
br s), 8.69 (1H, br). C NMR (CDCl3) ꢀ 30.56 (3C, p), 34.49 (1C,
q), 126.11 (1C, t), 126.21 (1C, t), 126.62 (1C, t), 126.88 (1C, t),
1
34.14 (1C, q), 141.84 (1C, q), 145.17 (1C, t), 160.00 (1C, q).
General Procedure for the Preparation of 7-Alkylisatins.
To a stirred mixture of concd H2SO4 (110 mL) and water (15 mL)
ꢂ
at 60 C was gradually added an N-(2-alkylphenyl)-2-hydroxyimi-
ꢂ
noacetamide (0.155 mol) and the mixture was kept at 65–70 C for
1
0 min. The mixture was poured onto ice-water and the precipi-
tates were collected by filtration and washed thoroughly with
water, air-dried, and recrystallized from dichloromethane.
7
-Ethylisatin: This compound was obtained in 81% yield, mp
ꢂ
17
ꢂ
1
1
93–194 C (lit. 189–190 C). H NMR (CDCl3) ꢀ 1.291 (3H, t,
J ¼ 7:6 Hz), 2.637 (2H, q, J ¼ 7:6 Hz), 7.081 (1H, t, J ¼ 7:6 Hz),
.431 (1H, dd, J ¼ 7:7, 0.6 Hz), 7.479 (1H, d, J ¼ 7:5 Hz), 9.37
1H, br s). 13C NMR (CDCl3) ꢀ 13.71 (1C, p), 22.66 (1C, s),
9-Cyano-1-methyltriptycene (24): Compound 24 was ob-
ꢂ
tained in 21% yield, mp 221–222 C. Anal. Found: C, 89.77; H,
5.26; N, 4.81%. Calcd for C22H15N: C, 90.07; H, 5.15; N, 4.77%.
7
(
1
H NMR (CDCl3) ꢀ 2.831 (3H, s), 5.386 (1H, s), 6.829 (1H, d,
1
1
17.66 (1C, q), 123.16 (1C, t), 124.02 (1C, t), 128.10 (1C, q),
38.24 (1C, t), 147.45 (1C, q), 160.81 (1C, q), 183.85 (1C, q).
J ¼ 7:7 Hz), 6.939 (1H, t, J ¼ 7:5 Hz), 7.08–7.18 (4H, m), 7.261
1
3
(1H, d, J ¼ 6:3 Hz), 7.422 (2H, m), 7.805 (2H, m). C NMR
(CDCl3) ꢀ 20.26 (1C, p), 51.91 (1C, q), 53.73 (1C, t), 118.50 (1C,
q), 122.25 (2C, t), 122.37 (1C, t), 123.75 (2C, t), 125.62 (2C, t),
126.26 (1C, t), 126.72 (2C, t), 129.37 (1C, t), 133.20 (1C, q),
137.69 (1C, q), 140.86 (2C, q), 143.50 (2C, q), 144.26 (1C, q).
10-Cyano-1-methyltriptycene (24a): Compound 24a was
7-Isopropylisatin:
ꢂ
This compound was obtained in 89%
18
ꢂ
1
yield, mp 196–198 C (lit. 187–191 C). H NMR (CDCl3) ꢀ
1
.306 (6H, d, J ¼ 6:9 Hz), 2.940 (1H, sept, J ¼ 6:9 Hz), 7.105
13
(1H, t, J ¼ 7:7 Hz), 7.45–7.51 (2H, m), 8.97 (1H, br). C NMR
(CDCl3) ꢀ 22.27 (2C, p), 27.60 (1C, t), 117.75 (1C, q), 123.18
(1C, t), 124.18 (1C, t), 132.60 (1C, q), 135.48 (1C, t), 146.76
(1C, q), 160.80 (1C, q), 183.92 (1C, q).
ꢂ
obtained in 20% yield, mp 206–208 C. Anal. Found: C, 90.40;
H, 5.24; N, 4.81%. Calcd for C22H15N: C, 90.07; H, 5.15; N,
1
7
-t-Butylisatin: This compound was obtained in 98% yield,
ꢂ
4.77%. H NMR (CDCl3) ꢀ 2.523 (3H, s), 5.672 (1H, s), 6.91–
7.03 (2H, m), 7.06–7.16 (4H, m), 7.422 (2H, m), 7.558 (1H, dm,
18
ꢂ
1
mp 236–238 C (lit. 227–230 C). H NMR (CDCl3) ꢀ 1.425
13
(
9H, s), 7.073 (1H, t, J ¼ 7:8 Hz), 7.491 (1H, d, J ¼ 7:5 Hz),
J ¼ 7:3 Hz), 7.701 (2H, m). C NMR (CDCl3) ꢀ 18.45 (1C, p),
49.24 (1C, t), 53.91 (1C, q), 116.31 (1C, q), 119.61 (1C, t), 121.81
(2C, t), 123.89 (2C, t), 125.22 (1C, t), 125.64 (2C, t), 126.57 (2C,
t), 128.21 (1C, t), 132.30 (1C, q), 140.34 (1C, q), 140.75 (2C, q),
141.45 (1C, q), 143.16 (2C, q).
1
3
7
ꢀ
1
1
.559 (1H, d, J ¼ 8:1 Hz), 8.944 (1H, br s). C NMR (CDCl3)
29.72 (3C, p), 34.06 (1C, q), 118.77 (1C, q), 123.36 (1C, t),
23.83 (1C, t), 134.41 (1C, q), 135.90 (1C, t), 146.75 (1C, q),
59.44 (1C, q), 183.61 (1C, q).
General Procedure for the Preparation of 3-Alkylanthranil-
9-Cyano-1-ethyltriptycene (25): Compound 25 was obtained

1
596 Bull. Chem. Soc. Jpn. Vol. 79, No. 10 (2006)
Deamination of 9-Aminomethyltriptycenes
ꢂ
in 16% yield, mp 181–191 C. Anal. Found: C, 89.57; H, 5.54; N,
1
General Procedure for the Preparation of 1-Alkyl-9-amino-
methyltriptycene (11–14). A mixture of 1-alkyl-9-cyanotripty-
cene (0.82 mmol) and LiAlH4 (93 mg, 2.5 mmol) in THF (30 mL)
4
.53%. Calcd for C23H17N: C, 89.87; H, 5.57; N, 4.56%. H NMR
(
5
CDCl3) ꢀ 1.312 (3H, t, J ¼ 7:5 Hz), 3.271 (2H, q, J ¼ 7:5 Hz),
ꢂ
.391 (1H, s), 6.861 (1H, dd, J ¼ 7:8, 1.3 Hz), 6.974 (1H, t, J ¼
under Ar was stirred for 15 h at 40–60 C. The mixture was
7
:5 Hz), 7.08–7.18 (4H, m), 7.258 (1H, dd, J ¼ 7:2, 1.4 Hz), 7.421
quenched with aq NaHCO3 and extracted with diethyl ether.
The extracts were washed with water and dried over MgSO4,
and the solvent was evaporated. The residue was recrystallized
from benzene–hexane.
1
3
(
(
(
(
(
2H, m), 7.817 (2H, m). C NMR (CDCl3) ꢀ 17.47 (1C, p), 26.10
1C, s), 51.67 (1C, q), 53.79 (1C, t), 118.32 (1C, q, CN), 122.25
2C, t), 122.30 (1C, t), 123.72 (2C, t), 125.62 (2C, t), 126.41
1C, t), 126.70 (2C, t), 128.04 (1C, t), 137.02 (1C, q), 139.66
1C, q), 140.83 (2C, q), 143.47 (2C, q), 144.33 (1C, q).
9-Aminomethyl-1-methyltriptycene (11): Compound 11 was
ꢂ
obtained in 65%, mp 181–183 C. Spectral data were completely
10-Cyano-1-ethyltriptycene (25a): Compound 25a was ob-
tained in 18% yield, mp 156–158 C. Anal. Found: C, 90.07; H,
identical with those for the sample of 11 synthesized by Route
A, described above.
9-Aminomethyl-1-ethyltriptycene (12): Compound 12 was
obtained in 59%, mp 144–146 C. Anal. Found: C, 88.52; H, 6.87;
N, 4.48%. Calcd for C23H21N: C, 88.71; H, 6.80; N, 4.50%.
ꢂ
5
.70; N, 4.63%. Calcd for C23H17N: C, 89.87; H, 5.57; N, 4.56%.
1
ꢂ
H NMR (CDCl3) ꢀ 1.269 (3H, t, J ¼ 7:6 Hz), 2.888 (2H, q, J ¼
7
:6 Hz), 5.694 (1H, s), 6.945 (1H, dd, J ¼ 7:7, 1.2 Hz), 7.029 (1H,
1
t, J ¼ 7:6 Hz), 7.06–7.16 (4H, m), 7.435 (2H, m), 7.570 (1H, dd,
H NMR (CDCl3) ꢀ 1.180 (3H, t, J ¼ 7:5 Hz), 1.66 (2H, br s),
1
3
J ¼ 7:4, 1.0 Hz), 7.702 (2H, m). C NMR (CDCl3) ꢀ 15.82 (1C,
2.88 (2H, br q, J ¼ 7:5 Hz), 4.72 (2H, br s), 5.292 (1H, s), 6.67–
6.88 (2H, br m), 7.00–7.19 (5H, br m), 7.42 (2H, br d, J ꢄ 8 Hz),
7.60 (2H, br). 13C NMR (CDCl3) ꢀ 17.95 (1C, p), 27.73 (1C, s),
41.25 (1C, s), 55.57 (1C, t), 58.96 (1C, q), 121.87 (1C, t), 123.16
(2C, t), 123.78 (2C, t), 124.85 (2C, t), 124.98 (1C, t), 125.46 (2C,
t), 128.39 (1C, t), 139.08 (1C, q), 142.99 (1C, q), 144.24 (2C, q),
p), 25.98 (1C, s), 48.95 (1C, t), 53.92 (1C, q), 116.32 (1C, q, CN),
1
1
1
19.68 (1C, t), 121.73 (2C, t), 123.75 (2C, t), 125.38 (1C, t),
25.56 (2C, t), 126.57 (2C, t), 126.84 (1C, t), 138.61 (1C, q),
40.37 (1C, q), 140.77 (2C, q), 141.04 (1C, q), 143.21 (2C, q).
9
-Cyano-1-isopropyltriptycene (26):
ꢂ
Compound 26 was
obtained in 21% yield, mp 215–217 C. Anal. Found: C, 89.38;
ꢂ
146.60 (2C, q), 149.34 (1C, q). The NMR spectra at ꢁ44 C reveal
H, 5.84; N, 4.39%. Calcd for C24H19N: C, 89.68; H, 5.96; N,
that rotation about the Tp-CH2NH2 bond is frozen and that ca.
1
1
ꢂ
4
.36%. H NMR (CDCl3) ꢀ 1.303 (6H, d, J ¼ 6:7 Hz), 4.480 (1H,
96% of 12 exist as the ap-rotamer: H NMR (CDCl3, ꢁ44 C) ꢀ
1.185 (3H, t, J ¼ 7:3 Hz), 1.987 (2H, br s), 2.881 (2H, q, J ¼ 7:3
Hz), 4.732 (2H, s), 5.382 (1H, s), 6.740 (1H, dd, J ¼ 7:8, 1.3 Hz),
6.860 (1H, t, J ¼ 7:6 Hz), 7.03–7.16 (4H, m), 7.191 (1H, dd,
J ¼ 7:2, 1.3 Hz), 7.494 (2H, m), 7.598 (2H, m). For the minor
sept, J ¼ 6:7 Hz), 5.391 (1H, s), 6.98–7.07 (2H, m), 7.08–7.18
(
(
(
(
4H, m), 7.248 (1H, dd, J ¼ 6:2, 2.3 Hz), 7.412 (2H, m), 7.829
2H, m). 13C NMR (CDCl3) ꢀ 24.34 (2C, p), 27.71 (1C, t), 51.57
1C, q), 54.02 (1C, t), 118.60 (1C, q, CN), 122.17 (1C, t), 122.35
2C, t), 123.19 (1C, t), 123.73 (2C, t), 125.68 (2C, t), 126.53 (1C,
ꢂ
ꢃsc isomer, the following signals were detected at ꢁ44 C: ꢀ
t), 126.76 (2C, t), 136.63 (1C, q), 140.93 (2C, q), 143.61 (2C, q),
44.15 (1C, q), 144.17 (1C, q).
1.118 (3H, t, J ¼ 7:3 Hz), 4.323 (1H, d, J ¼ 12:4 Hz), 4.574
(1H, d, J ¼ 12:4 Hz), 5.329 (1H, s).
1
10-Cyano-1-isopropyltriptycene (26a): Compound 26a was
obtained in 19% yield, mp 251–253 C. Anal. Found: C, 89.30; H,
9-Aminomethyl-1-isopropyltriptycene (13): Compound 13
ꢂ
ꢂ
was obtained in 93% yield, mp 108–109 C. Anal. Found: C,
88.85; H, 6.83; N, 4.37%. Calcd for C24H23N: C, 88.57; H, 7.12;
6
.08; N, 4.38%. Calcd for C24H19N: C, 89.68; H, 5.96; N, 4.36%.
1
1
H NMR (CDCl3) ꢀ 1.304 (6H, d, J ¼ 6:9 Hz), 3.511 (1H, sept,
J ¼ 6:9 Hz), 5.798 (1H, s), 6.98–7.13 (6H, m), 7.424 (2H, m),
N, 4.30%. H NMR (CDCl3) ꢀ 1.204 (6H, d, J ¼ 6:3 Hz), 1.65
(2H, br s), 3.70 (1H, m), 4.748 (2H, br s), 5.282 (1H, s), 6.82–
1
3
7
.572 (1H, dd, J ¼ 6:6, 2.0 Hz), 7.701 (2H, m). C NMR (CDCl3)
6.98 (2H, br m), 7.00–7.16 (5H, br m), 7.43 (2H, br d, J ꢄ 6 Hz),
13
ꢀ 23.19 (2C, p), 29.68 (1C, q), 48.79 (1C, t), 54.08 (1C, q), 116.37
1C, q, CN), 119.71 (1C, t), 121.90 (2C, t), 123.22 (1C, t), 123.85
7.58 (2H, br d, J ꢄ 6 Hz). C NMR (CDCl3) ꢀ 24.76 (2C, p),
28.85 (1C, t), 41.73 (1C, s), 55.70 (1C, t), 59.11 (1C, q), 121.82
(1C, t), 123.15 (2C, t), 123.37 (1C, t), 123.81 (2C, t), 124.89
(2C, t), 125.04 (1C, t), 125.38 (2C, t), 142.28 (1C, q), 144.01
(3C, q), 146.55 (2C, q), 149.07 (1C, q).
(
(2C, t), 125.60 (1C, t), 125.70 (2C, t), 126.66 (2C, t), 140.29 (1C,
q), 140.76 (1C, q), 140.98 (2C, q), 142.84 (1C, q), 143.33 (2C, q).
1-t-Butyl-9-cyanotriptycene (27): Compound 27 was ob-
tained in 45% yield, mp 250–252 C. Anal. Found: C, 89.58; H,
ꢂ
1-t-Butyl-9-phthalimidomethyltriptycene (30). To a boiling
solution of 9-phthalimidomethylanthracene20 (0.30 g, 0.89 mmol)
in 1,2-dichloroethane (5 mL) were added simultaneously a solu-
tion of isopentyl nitrite (0.83 mL, 6.2 mmol) in of 1,2-dichloro-
ethane (50 mL) and a solution of 3-t-butylanthranilic acid (22d)
(0.86 g, 4.5 mmol) in THF (50 mL) during the course of 3 h, and
the mixture was stirred under reflux for 2 h. Column chromatogra-
phy on silica gel with benzene–hexane (1:1) as the eluent afforded
a mixture of 30 and its regioisomer, 1-t-butyl-10-phthalimido-
methyltriptycene (30a) in a ratio of ca. 2:3. Each isomer was iso-
lated by GPC of the mixture. Compound 30 was obtained in 9%
6
.34; N, 4.14%. Calcd for C25H21N: C, 89.51; H, 6.31; N, 4.18%.
1
H NMR (CDCl3) ꢀ 1.651 (9H, s), 5.404 (1H, s), 6.984 (1H, dd,
J ¼ 8:0, 7.3 Hz), 7.08–7.20 (5H, m), 7.293 (1H, dd, J ¼ 7:3,
1
3
1
.2 Hz), 7.429 (2H, m), 7.903 (2H, m). C NMR (CDCl3) ꢀ 34.31
3C, p), 35.39 (1C, q), 53.51 (1C, q), 54.83 (1C, t), 119.82 (1C, q,
(
CN), 122.95 (2C, t), 123.10 (1C, t), 123.61 (2C, t), 123.77 (1C, t),
1
1
25.72 (2C, t), 126.02 (1C, t), 126.88 (2C, t), 138.99 (1C, q),
40.63 (2C, q), 143.81 (2C, q), 145.71 (1C, q), 146.39 (1C, q).
1
-t-Butyl-10-cyanotriptycene (27a):
ꢂ
Compound 27a was
obtained in 23% yield, mp 269–270 C. Anal. Found: C, 89.13;
ꢂ
H, 6.46; N, 4.23%. Calcd for C25H21N: C, 89.51; H, 6.31; N,
yield, mp 254–255 C (from ethyl acetate). Anal. Found: C, 84.79;
H, 5.75; N, 3.05%. C33H27NO2: C, 84.41; H, 5.80; N, 2.98%.
1
4
.18%. H NMR (CDCl3) ꢀ 1.550 (9H, s), 6.248 (1H, s), 7.027
1
(
7
ꢀ
1H, dd, J ¼ 8:1, 7.5 Hz), 7.06–7.16 (5H, m), 7.440 (2H, m),
H NMR (CDCl3) ꢀ 1.661 (9H, s), 5.356 (1H, s), 5.944 (2H, s),
1
3
.636 (1H, dd, J ¼ 7:5, 1.2 Hz), 7.703 (2H, m). C NMR (CDCl3)
6.823 (1H, dd, J ¼ 8:1, 7.1 Hz), 6.907 (2H, td, J ¼ 7:6, 1.3 Hz),
7.040 (2H, td, J ¼ 7:4, 1.0 Hz), 7.144 (1H, dd, J ¼ 8:2, 1.3 Hz),
7.207 (1H, dd, J ¼ 7:1, 1.3 Hz), 7.278 (2H, d, J ¼ 7:6 Hz), 7.451
31.42 (3C, p), 35.47 (1C, q), 51.01 (1C, t), 54.34 (1C, q), 116.48
(
1C, q, CN), 120.36 (1C, t), 121.86 (2C, t), 123.79 (2C, t), 124.00
1C, t), 125.20 (1C, t), 125.70 (2C, t), 126.64 (1C, t), 141.14 (2C,
13
(
q), 141.30 (1C, q), 141.99 (1C, q), 142.84 (2C. q), 145.33 (1C, q).
(2H, dd, J ¼ 7:3, 1.0 Hz), 7.60–7.72 (4H, m). C NMR (CDCl3) ꢀ
35.12 (3C, p), 35.42 (1C, q), 46.42 (1C, s), 53.57 (1C, t), 56.79

G. Yamamoto et al.
Bull. Chem. Soc. Jpn. Vol. 79, No. 10 (2006) 1597
(
(
(
(
(
1C, q), 122.30 (2C, t), 122.94 (1C, t), 123.12 (2C, t), 123.42
2C, t), 124.27 (1C, t), 124.29 (1C, t), 124.66 (2C, t), 125.46
2C, t), 131.80 (2C, q), 133.83 (2C, t), 143.58 (2C, q), 145.19
1C, q), 145.70 (2C, q), 147.09 (1C, q), 150.56 (1C, q), 168.00
2C, q).
88.31; H, 6.82; N, 4.50%. Calcd for C23H21N: C, 88.71; H, 6.80;
N, 4.50%. H NMR (CDCl3) revealed the presence of two rotam-
1
ꢀ
ꢀ
ꢀ
ers, R -ðꢁscÞ and ap, in a ratio of 64:36; the R -ðꢁscÞ isomer: ꢀ
1.90 (2H, br, NH2), 1.968 (3H, d, J ¼ 6:5 Hz), 2.786 (3H, s),
5.164 (1H, q, J ¼ 6:5 Hz), 5.217 (1H, s), 6.73–7.50 (10H, m),
8.274 (1H, d, J ¼ 7:7 Hz); the ap isomer: ꢀ 1.90 (2H, br), 2.090
(3H, d, J ¼ 6:5 Hz), 2.566 (3H, s), 5.209 (1H, q, J ¼ 6:5 Hz),
5.221 (1H, s), 6.74–7.59 (10H, m), 8.046 (1H, d, J ¼ 7:7 Hz).
ꢂ
Compound 30a was obtained in 9% yield, mp 189–191 C
from CHCl3–hexane). Anal. Found: C, 84.21; H, 5.55; N, 3.02%.
(
Calcd for C33H27NO2: C, 84.41; H, 5.80; N, 2.98%. 1H NMR
13
ꢀ
(
(
7
CDCl3) ꢀ 1.594 (9H, s), 5.237 (2H, s), 6.251 (1H, s), 6.890
1H, t, J ¼ 7:7 Hz), 6.92–7.03 (4H, m), 7.054 (1H, d, J ¼ 7:9 Hz),
C NMR (CDCl3): the R -ðꢁscÞ isomer: ꢀ 21.74 (1C, p), 22.58
(1C, p), 46.12 (1C, s), 56.32 (1C, t), 62.14 (1C, q), 122.05 (1C, t),
123.44 (1C, t), 123.48 (1C, t), 123.52 (1C, t), 123.95 (1C, t),
124.51 (1C, t), 124.62 (1C, t), 124.67 (1C, t), 125.48 (1C, t),
128.06 (1C, t), 130.37 (1C, t), 132.34 (1C, t), 142.16 (1C, q),
144.03 (1C, q), 145.69 (1C, q), 146.69 (1C, q), 148.31 (1C, q),
149.34 (1C, q); the ap isomer: ꢀ 23.09 (1C, p), 24.38 (1C, p),
46.27 (1C, s), 56.34 (1C, t), 62.91 (1C, q), 121.74 (1C, t),
122.48 (1C, t), 123.78 (1C, t), 123.80 (1C, q), 124.11 (1C, t),
124.50 (1C, t), 124.94 (1C, t), 125.57 (1C, t), 126.96 (1C, t),
130.29 (1C, t), 132.64 (1C, t), 142.28 (1C, q), 144.29 (1C, q),
146.16 (1C, q), 146.82 (1C, q), 148.48 (1C, q), 149.18 (1C, q),
one tertiary peak missing.
.194 (1H, d, J ¼ 7:6 Hz), 7.274 (2H, m), 7.429 (2H, m), 7.724
13
(
2H, m), 7.826 (2H, m). C NMR (CDCl3) ꢀ 31.63 (3C, p), 35.45
(
1C, q), 43.05 (1C, s), 51.13 (1C, t), 51.86 (1C, q), 119.74 (1C, t),
1
1
1
1
21.48 (2C, t), 122.43 (1C, t), 123.33 (2C, t), 123.37 (2C, t),
24.10 (1C, t), 124.75 (2C, t), 125.05 (2C, t), 131.94 (2C, q),
34.02 (2C, t), 144.21 (1C, q), 144.32 (1C, q), 144.84 (2C, q),
46.24 (2C, q), 146.51 (1C, q), 168.01 (2C, q).
1
-t-Butyl-9-aminomethyltriptycene (14). A mixture of 30
300 mg, 0.32 mmol) and hydrazine hydrate (240 mL, 4.93 mmol)
in THF (3 mL) and ethanol (2 mL) was heated under reflux for
h. The solvent was evaporated and the residue was extracted
(
7
with CHCl3. The CHCl3 solution was washed with water and
dried over MgSO4 and the solvent was evaporated. Recrystalliza-
Deamination Reactions. The reactions were systematically
run as follows. To a magnetically stirred solution of the amine
(2 mmol) in the appropriate solvent (CHCl3 containing 1.2 molar
amount of AcOH or AcOH) (10 mL) was added 1.1 molar amount
ꢂ
tion from hexane gave 173 mg (81%) of 14, mp 159–162 C. Anal.
Found: C, 88.50; H, 7.12; N, 4.21%. Calcd for C25H25N: C, 88.45;
1
ꢂ
H, 7.42; N, 4.13%. H NMR (CDCl3) ꢀ 1.530 (9H, s), 1.60 (2H,
of isopentyl nitrite at 23 C and the solution was stirred for 4 h.
br s), 4.901 (2H, s), 5.285 (1H, s), 6.801 (1H, dd, J ¼ 8:1, 7.1 Hz),
After the starting amine was completely consumed, the mixture
was extracted with diethyl ether, and the extracts were washed
with water and brine, and dried over MgSO4. After evaporation
of the solvent, the residue was submitted to NMR analysis to de-
termine the product ratio. The product ratios reported are the aver-
ages from two or three experiments under the same conditions.
The mixture was then submitted to preparative GPC to isolate
and characterize each product. Characterization of the products
was mainly made by analysis of the H and 13C NMR spectra. El-
emental analysis was made when a sufficient amount of the sam-
ple was obtained.
7
.01–7.13 (5H, m), 7.155 (1H, dd, J ¼ 7:1, 1.3 Hz), 7.435 (2H,
13
m), 7.540 (2H, m). C NMR (CDCl3) ꢀ 34.85 (3C, p), 35.32
1C, q), 42.91 (1C, s), 56.83 (1C, t), 59.17 (1C, q), 122.79 (1C, t),
(
1
1
1
23.50 (2C, t), 123.88 (2C, t), 124.02 (1C, t), 124.22 (1C, t),
25.00 (2C, t), 125.54 (2C, t), 143.94 (2C, q), 145.24 (1C, q),
46.83 (2C, q), 147.35 (1C, q), 150.97 (1C, q).
9-(1-Iminoethyl)-1-methyltriptycene (28). To a solution of
4 (0.60 g, 1.95 mmol) in anhydrous diethyl ether (30 mL) was
1
2
added under argon 1 M methyllithium (12 mL, 12 mmol) in diethyl
ether, and the mixture was stirred for 3 h at room temperature. Af-
ter quenching with water, the mixture was extracted with diethyl
ether. The extracts were dried over MgSO4 and the solvent was
1,2,6,10b-Tetrahydro-6,10b-o-benzenoaceanthrylene (31):
ꢂ
Mp 207–209 C. Anal. Found: C, 94.20; H, 5.82%. Calcd for
1
evaporated. Recrystallization from dichloromethane–hexane gave
C22H16: C, 94.25; H, 5.75%. H NMR (CDCl3) ꢀ 3.25 (2H, m,
ꢂ
0
8
.56 g (1.81 mmol, 93%) of 28, mp 192–194 C. Anal. Found: C,
8.95; H, 6.13; N, 4.57%. Calcd for C23H19N: C, 89.28; H, 6.19;
1-H), 3.35 (2H, m, 2-H), 5.462 (1H, s), 6.869 (1H, dd, J ¼ 7:6,
0.8 Hz), 6.90–7.03 (5H, m), 7.189 (1H, dd, J ¼ 7:0, 0.7 Hz), 7.31–
1
13
N, 4.53%. H NMR (CDCl3) at ambient temperature gave broad-
ened signals, presumably because of syn–anti isomerization of the
NH moiety: ꢀ 2.44 (3H, br s), 2.54 (3H, br s), 5.26 (1H, s), 6.81
7.44 (4H, m). C NMR (CDCl3) ꢀ 22.83 (1C, s, 1-C), 33.18 (1C,
s, 2-C), 53.75 (1C, t), 60.05 (1C, q), 120.32 (1C, t), 120.37 (2C, t),
121.24 (1C, t), 123.98 (2C, t), 124.58 (2C, t), 124.74 (2C, t),
126.37 (1C, t), 136.47 (1C, q), 141.72 (1C, q), 146.33 (2C, q),
147.64 (2C, q), 152.37 (1C, q).
(
7
1H, d, J ¼ 7:7 Hz), 6.91 (1H, t, J ¼ 7:4 Hz), 6.98–7.03 (4H, m),
.23 (1H, d, J ¼ 7:0 Hz), 7.35 (2H, br d, J ¼ 6:5 Hz), 8.10 (2H,
ꢂ
br), 10.22 (1H, br, NH). At ca. ꢁ30 C, two isomers were ob-
1,2,6,10b-Tetrahydro-6,10b-o-benzenoaceanthrylene-2,2-d2
þ
1
served in a ratio of 78:22. The major isomer: ꢀ 2.473 (3H, s),
(31a): MS m=z 282 (M ). H NMR (CDCl3) ꢀ 3.25 (2H, m),
5.462 (1H, s), 6.869 (1H, dd, J ¼ 7:6, 0.8 Hz), 6.90–7.03 (5H, m),
2
.535 (3H, s), 5.319 (1H, s), 6.837 (1H, d, J ¼ 7:5 Hz), 6.947 (1H,
t, J ¼ 7:5 Hz), 6.97–7.07 (4H, m), 7.273 (1H, d, J ¼ 7:5 Hz),
.382 (2H, d, J ¼ 7:0 Hz), 8.111 (2H, d, J ¼ 7:0 Hz), 10.225 (1H,
s, NH). The minor isomer: ꢀ 2.317 (3H, s), 2.862 (3H, s), 5.32
1
3
7.189 (1H, dd, J ¼ 7:0, 0.7 Hz), 7.31–7.44 (4H, m). C NMR
(CDCl3) ꢀ 22.60 (1C, s), 32.54 (1C, quint, J ¼ 18:8 Hz), 53.72
(1C, t), 60.04 (1C, q), 120.33 (1C, t), 120.35 (2C, t), 121.27 (1C,
t), 123.97 (2C, t), 124.57 (2C, t), 124.73 (2C, t), 126.34 (1C, t),
136.34 (1C, q), 141.69 (1C, q), 146.31 (2C, q), 147.64 (2C, q),
152.43 (1C, q).
7
(
1H, s), 6.8–7.6 (11H, m), 9.957 (1H, s, NH).
-(1-Aminoethyl)-1-methyltriptycene (15). To a solution of
8 (220 mg, 0.71 mmol) in dry THF (20 mL) was added 270 mg
9
2
(
7.11 mmol) of LiAlH4 under argon and the mixture was heated
1-Acetoxymethyl-9-methyltriptycene (32):
Oil. 1H NMR
under reflux for 24 h. After quenching with aq NaHCO3, the mix-
ture was extracted with diethyl ether. The extracts were washed
with water and dried over MgSO4 and the solvent was evaporated.
(CDCl3) ꢀ 2.077 (3H, s), 2.652 (3H, s), 5.382 (1H, s), 5.391
13
(2H, s), 6.92–7.08 (6H, m), 7.34–7.43 (5H, m). C NMR (CDCl3)
ꢀ 16.18 (1C, p), 21.12 (1C, p), 51.25 (1C, q), 54.94 (1C, t), 65.18
(1C, s), 121.38 (2C, t), 123.19 (2C, t), 124.73 (1C, t), 125.03 (2C,
t), 125.22 (1C, t), 125.24 (2C, t), 129.51 (1C, t), 130.54 (1C, q),
The residue was recrystallized from diethyl ether–hexane to afford
ꢂ
1
22 mg (0.39 mmol, 55%) of 15, mp 191–193 C. Anal. Found: C,

1
598 Bull. Chem. Soc. Jpn. Vol. 79, No. 10 (2006)
Deamination of 9-Aminomethyltriptycenes
1
1
44.99 (1C, q), 145.99 (2C, q), 147.33 (2C, q), 148.47 (1C, q),
70.68 (1C, q).
of the vinyl group were ‘‘deceptively simple,’’ and spectral simu-
lation (LAOCN3 ) was necessary for the analysis: ꢀa ¼ 7:465,
2
1
1
-Acetoxy(methyl-d2)-9-(methyl-d)triptycene (32a):
MS
m=z 343 (M ). H NMR (CDCl3) ꢀ 2.079 (3H, s), 2.636 (2H, s),
.386 (1H, s), 6.92–7.08 (6H, s), 7.34–7.43 (5H, m).
0-Acetoxy-10,11-dihydro-1-methyl-5,10-o-benzeno-5H-di-
ꢀ
b ¼ 5:275, ꢀc ¼ 5:287, Jab ¼ 10:9 Hz, Jac ¼ 17:0 Hz, and Jbc ¼
þ
1
a b c 13
1:8 Hz for –CH =CH H . C NMR (CDCl3) ꢀ 18.21 (1C, p),
51.33 (1C, q), 54.82 (1C, t), 116.67 (1C, s), 121.34 (2C, t), 123.12
(2C, t), 123.40 (1C, t), 124.89 (2C, t), 125.08 (2C, t), 125.17 (2C,
t), 127.28 (1C, t), 136.04 (1C, q), 138.49 (1C, t), 142.55 (1C, q),
5
1
ꢂ
1
benzo[a,d]cycloheptene (33):
(
Mp 273–286 C. H NMR
CDCl3) ꢀ 2.035 (3H, s), 2.462 (3H, s, OAc), 3.116 (2H, br s),
146.14 (2C, q), 147.39 (1C, q), 147.65 (2C, q).
1-Isopropenyl-9-methyltriptycene (42):
ꢂ
4
.895 (1H, s), 6.901 (1H, d, J ¼ 7:0 Hz), 6.972 (1H, t, J ¼ 7:0
Mp 160–162 C.
1
3
Hz), 7.12–7.26 (7H, m), 7.365 (2H, m). C NMR (CDCl3) ꢀ
9.74 (1C, p), 22.04 (1C, p), 42.30 (1C, s), 54.63 (1C, t), 122.25
2C, t), 124.99 (1C, t), 125.11 (2C, t), 126.30 (1C, t), 126.42 (2C,
t), 127.24 (2C, t), 128.90 (1C, t), 131.20 (1C, q), 137.69 (2C, q),
38.80 (1C, q), 139.13 (2C, q), 140.34 (1C, q), 168.49 (1C, q). At
Anal. Found: C, 93.84; H, 6.26%. Calcd for C24H20: C, 93.46;
1
1
(
H, 6.54%. H NMR (CDCl3) ꢀ 2.057 (3H, t, J ¼ 1:0 Hz), 2.524
(3H, s, 9-Me), 4.808 (1H, m), 5.212 (1H, m), 5.357 (1H, s, 10-H),
6.643 (1H, dd, J ¼ 7:7, 1.4 Hz), 6.878 (1H, t, J ¼ 7:5 Hz), 6.95–
7.04 (4H, m), 7.252 (1H, dd, J ¼ 7:2, 1.3 Hz), 7.31–7.40 (4H, m).
1
13
room temperature, the methylene proton signal appeared as a
broad singlet (W1=2 ꢄ 20 Hz in CDCl3) together with some broad-
ening of the other signals. The methylene signal sharpened upon
either elevating or lowering the temperatures (W1=2 ꢄ 3 Hz at 60
C NMR (CDCl3) ꢀ 16.06 (1C, p), 27.38 (1C, p), 50.80 (1C, q),
54.88 (1C, t), 115.50 (1C, s), 121.10 (1C, t), 121.29 (1C, t), 122.51
(1C, t), 123.11 (1C, t), 123.16 (1C, t), 124.47 (1C, t), 124.91 (1C,
t), 129.92 (1C, t), 125.01 (1C, t), 125.02 (1C, t), 127.39 (1C, t),
140.16 (1C, q), 141.81 (1C, q), 146.04 (1C, q), 146.19 (1C, q),
146.79 (1C, q), 147.47 (1C, q), 147.69 (1C, q), 147.91 (1C, q).
3,3-Dimethyl-2,3,7,11b-tetrahydro-7,11b-o-benzeno-1H-ben-
ꢂ
and ꢁ35 C), presumably reflecting the rotation of the C–OAc
ꢂ
bond. At 60 C the rotation is fast on the NMR timescale, while
ꢂ
at ꢁ35 C the rotation is slow but the rotamer equilibrium is
ꢂ
almost shifted to the ap rotamer.
zo[d,e]anthracene (46): Mp 154–157 C. Anal. Found: C, 93.23;
1
2
-Methyl-1,2,6,10b-tetrahydro-6,10b-o-benzenoaceanthryl-
ꢂ
H, 6.70%. Calcd for C25H22: C, 93.12; H, 6.88%. H NMR
1
ene (38): Mp 165–167 C. H NMR (CDCl3) ꢀ 1.425 (3H, d,
J ¼ 7:1 Hz), 2.792 (1H, dd, J ¼ 14:2, 5.4 Hz), 3.509 (1H, dd, J ¼
(CDCl3) ꢀ 1.300 (6H, s), 2.000 (2H, m, 2-H), 3.035 (2H, m, 1-H),
5.362 (1H, s), 6.927 (1H, dd, J ¼ 7:8, 7.2 Hz), 6.95–7.04 (5H, m),
7.192 (1H, dd, J ¼ 7:2, 1.2 Hz), 7.360 (2H, dd, J ¼ 7:2, 1.2 Hz),
1
4:2, 8.7 Hz), 3.717 (1H, m), 5.468 (1H, s), 6.851 (1H, d, J ¼ 7:7
13
Hz), 6.92–7.04 (5H, m), 7.205 (1H, d, J ¼ 7:7 Hz), 7.33–7.43
7.380 (2H, d, J ¼ 7:8 Hz). C NMR (CDCl3) ꢀ 20.14 (1C, s),
30.09 (2C, p), 33.63 (1C, q), 36.01 (1C, s), 49.47 (1C, q), 54.17
(1C, t), 120.92 (2C, t), 122.07 (1C, t), 123.53 (2C, t), 124.78
(2C, t), 124.81 (3C, t), 124.91 (1C, t), 140.85 (1C, q), 143.50
(
(
4H, m). 13C NMR (CDCl3) ꢀ 21.78 (1C, p), 32.66 (1C, s), 41.37
1C, t), 53.68 (1C, t), 59.07 (1C, q), 120.28 (1C, t), 120.35 (1C, t),
1
1
1
1
20.47 (1C, t), 120.59 (1C, t), 123.93 (1C, t), 124.00 (1C, t),
24.55 (2C, t), 124.72 (1C, t), 124.82 (1C, t), 126.45 (1C, t),
41.23 (1C, q), 141.70 (1C, q), 146.12 (1C, q), 146.42 (1C, q),
47.36 (1C, q), 148.35 (1C, q), 151.74 (1C, q).
(2C, q), 145.42 (1C, q), 146.82 (2C, q), 146.95 (1C, q).
ꢂ
1-Methyl-9-vinyltriptycene (51):
Mp 163–164 C. Anal.
Found: C, 93.62; H, 6.30%. Calcd for C23H18: C, 93.84; H, 6.16%.
1
1-(1-Acetoxyethyl)-9-methyltriptycene (39): Mp 201–202
H NMR (CDCl3) ꢀ 2.583 (3H, s), 5.322 (1H, s), 5.801 (1H, dd,
ꢂ
C. Anal. Found: C, 84.51; H, 6.19%. Calcd for C25H22O2: C,
J ¼ 18:3, 1.2 Hz), 6.151 (1H, dd, J ¼ 11:7, 1.2 Hz), 6.730 (1H,
dm, J ¼ 7:6 Hz), 6.836 (1H, t, J ¼ 7:5 Hz), 6.98–7.04 (4H, m),
7.202 (1H, dm, J ¼ 6:8 Hz), 7.394 (2H, m), 7.396 (1H, dd, J ¼
18:3, 11.7 Hz), 7.642 (2H, m). 13C NMR (CDCl3) ꢀ 23.99 (1C,
p), 55.39 (1C, t), 58.32 (1C, q), 120.84 (1C, s, =CH2), 121.97
(1C, t), 123.42 (2C, t), 123.66 (2C, t), 124.57 (2C, t), 124.89
(1C, t), 125.21 (2C, t), 129.89 (1C, t), 133.10 (1C, q), 134.52
(1C, t, –CH=), 144.32 (1C, q), 145.99 (2C, q), 146.00 (2C, q),
147.44 (1C, q).
1
8
4.72; H, 6.26%. H NMR (CDCl3) ꢀ 1.457 (3H, d, J ¼ 6:6 Hz),
.014 (3H, s), 2.740 (3H, s), 5.345 (1H, s), 6.93–7.08 (6H, m),
.187 (1H, dd, J ¼ 8:1, 1.4 Hz), 7.282 (1H, dd, J ¼ 7:2, 1.4 Hz),
2
7
7
1
3
.32–7.50 (4H, m). C NMR (CDCl3) ꢀ 18.07 (1C, p), 21.32
(1C, p), 24.00 (1C, p), 51.19 (1C, q), 55.07 (1C, t), 67.87 (1C,
t), 121.22 (1C, t), 121.72 (1C, t), 123.04 (1C, t), 123.17 (1C, t),
1
1
1
1
23.43 (1C, t), 123.87 (1C, t), 125.01 (1C, t), 125.11 (1C, t),
25.20 (1C, t), 125.24 (1C, t), 125.40 (1C, t), 138.59 (1C, q),
41.59 (1C, q), 145.70 (1C, q), 146.19 (1C, q), 147.14 (1C, q),
47.59 (1C, q), 147.67 (1C, q), 170.36 (1C, q).
9-(1-Acetoxyethyl)-1-methyltriptycene (52): Mp 214–216
C. 1H NMR (CDCl3) showed the presence of two rotamers,
ꢂ
ꢀ
ꢀ
ꢀ
ꢀ
1-(1-Hydroxyethyl)-9-methyltriptycene (40): Mp 207–208
R -ðꢁscÞ and ap, in a ratio of 72:28; the R -ðꢁscÞ isomer: ꢀ
2.054 (3H, d, J ¼ 5:9 Hz), 2.251 (3H, s), 2.381 (3H, s), 5.258
(1H, s), 6.666 (1H, q, J ¼ 5:9 Hz), 6.69–7.47 (11H, m), 7.881
(1H, d, J ¼ 7:7 Hz); the ap isomer: ꢀ 2.126 (3H, s), 2.189 (3H,
d, J ¼ 6:4 Hz), 2.578 (3H, s), 5.258 (1H, s), 6.75–7.47 (11H,
m), 6.944 (1H, q, J ¼ 6:1 Hz), 7.902 (1H, d, J ¼ 7:9 Hz).
ꢂ
C. Anal. Found: C, 88.20; H, 6.52%. Calcd for C23H20O: C,
1
8
8.43; H, 6.45%. H NMR (CDCl3) ꢀ 1.460 (3H, d, J ¼ 6:3 Hz),
.578 (1H, br s), 2.688 (3H, s), 5.359 (1H, s), 5.920 (1H, q, J ¼
:3 Hz), 6.98–7.10 (5H, m), 7.292 (1H, dd, J ¼ 7:2, 1.3 Hz), 7.34–
.43 (5H, m). 13C NMR (CDCl3) ꢀ 18.01 (1C, p), 25.90 (1C, p),
1.21 (1C, q), 55.14 (1C, t), 65.10 (1C, t), 121.22 (1C, t), 121.47
1
6
7
5
10-Acetoxy-10,11-dihydro-1,11-dimethyl-5,10-o-benzeno-5H-
1
(1C, t), 122.88 (1C, t), 123.14 (1C, t), 123.18 (1C, t), 123.36 (1C,
t), 124.96 (1C, t), 124.99 (1C, t), 125.21 (1C, t), 125.28 (1C, t),
dibenzo[a,d]cycloheptene (53): H NMR (CDCl3) ꢀ 1.439 (3H,
d, J ¼ 6:9 Hz), 2.404 (3H, s, OAc), 2.549 (3H, s), 3.369 (1H,
1
3
1
1
25.52 (1C, t), 141.68 (1C, q), 142.26 (1C, q), 146.00 (1C, q),
46.16 (1C, q), 147.38 (1C, q), 147.53 (1C, q), 147.77 (1C, q).
q, J ¼ 6:9 Hz), 4.809 (1H, s), 6.90–7.40 (11H, m). C NMR
(CDCl3) ꢀ 19.12 (1C, p), 21.44 (1C, p), 22.37 (1C, p), 46.32
(1C, t), 55.80 (1C, t), 85.49 (1C, q), 123.03 (1C, t), 124.27 (1C, t),
124.30 (1C, t), 126.14 (1C, t), 126.34 (1C, t), 126.66 (1C, t),
126.79 (1C, t), 126.98 (1C, t), 127.11 (1C, t), 131.20 (1C, t),
131.70 (1C, t), 133.46 (1C, q), 135.19 (1C, q), 138.58 (1C, q),
138.65 (1C, q), 139.26 (1C, q), 140.38 (1C, q), 140.97 (1C, q),
169.05 (1C, q).
ꢂ
9-Methyl-1-vinyltriptycene (41):
Mp 194–195 C. Anal.
Found: C, 93.67; H, 6.26%. Calcd for C23H18: C, 93.84; H, 6.16%.
1
H NMR (CDCl3) ꢀ 2.567 (3H, s), 5.24–5.30 (2H, m, =CH2),
5
.357 (1H, s), 6.883 (1H, dd, J ¼ 7:8, 2.0 Hz), 6.924 (1H, dd,
J ¼ 7:9, 7.1 Hz), 6.97–7.07 (4H, m), 7.297 (1H, dd, J ¼ 7:1,
.0 Hz), 7.33–7.40 (4H, m), 7.462 (1H, m, –CH=). The signals
2

G. Yamamoto et al.
Bull. Chem. Soc. Jpn. Vol. 79, No. 10 (2006) 1599
Table 1. Crystal Data and Parameters for Data Collection, Structure Determination, and Refinement
2
6
30
46
54
Empirical formula
C24H19N
321.40
monoclinic
P21=c
C33H27NO2
469.56
trigonal
C25H22
322.43
monoclinic
P21=n
C25H22O2
354.45
monoclinic
P21=a
Formula weight
Crystal system
Space group
ꢀ
R3
˚
a/A
10.8472(14)
13.2857(14)
12.4932(13)
90.00
100.5072(17)
90.00
1770.2(3)
4
1.206
0.069
293(2)
55.0
29.2779(9)
29.2779(9)
15.1293(5)
90.00
10.2269(9)
10.0974(7)
16.5762(11)
90.00
90.7078(14)
90.00
1711.6(2)
4
1.251
0.070
113(2)
55.0
10.075(5)
17.790(6)
10.915(6)
90.00
106.86(4)
90.00
1872(1)
4
1.257
0.078
296(2)
55.0
˚
b/A
˚
c/A
ꢂ
ꢂ
ꢂ
ꢁ/
ꢃ/
ꢄ/
90.00
120.00
11231.3(6)
18
1.250
0.077
˚
3
V/A
Z
ꢁ
3
Dcalcd/g cm
ꢁ
1
ꢅ(Mo Kꢁ)/cm
Temp/K
max/
No. of reflections measured
113(2)
55.0
ꢂ
2ꢆ
Total
Unique
3178
3052
5004
4440
3110
2909
4676
4289
No. of refinement variables
aÞ
229
0.0592; 0.1565
1.114
337
0.0518, 0.1516
1.053
229
0.0443, 0.1158
1.096
245
0.071; 0.104
1.206
bÞ
Final R1; wR2
GOF
2
2
2 2 1=2
a) R1 ¼ ꢁjjFoj ꢁ jFcjj=ꢁjFoj. b) wR2 ¼ fꢁ½wðFo ꢁ Fc Þꢅ=ꢁ½wðFo Þ ꢅg
.
ꢀ
ꢀ
ꢀ
,10-o-benzeno-5H-dibenzo[a,d]cycloheptene (54): Mp 231–
(
5R ,10R ,11R )-10-Acetoxy-10,11-dihydro-9,11-dimethyl-
Carbonium Ions, ed. by G. A. Olah, P. von R. Schleyer, 1970,
Vol. 2, Chap. 16.
5
ꢂ
1
2
34 C. H NMR (CDCl3) ꢀ 1.228 (3H, d, J ¼ 6:9 Hz), 2.397 (3H,
2
3
4
5
S. J. Cristol, D. K. Pennelle, J. Org. Chem. 1970, 35, 2357.
J. W. Wilt, T. P. Malloy, J. Org. Chem. 1972, 37, 2781.
¯
G. Yamamoto, M. Oki, Chem. Lett. 1987, 1163.
See for example: K. Hiraoka, R. Kebarle, J. Am. Chem.
s, OAc), 2.499 (3H, s), 3.550 (1H, q, J ¼ 6:9 Hz), 4.786 (1H, s),
1
3
6
.90–7.40 (11H, m). C NMR (CDCl3) ꢀ 18.99 (1C, p), 21.28
1C, p), 21.92 (1C, p), 42.59 (1C, t), 55.50 (1C, t), 84.47 (1C, q),
(
1
1
1
1
1
22.83 (1C, t), 125.37 (1C, t), 125.44 (1C, t), 125.61 (1C, t),
26.27 (1C, t), 126.79 (2C, t), 126.94 (1C, t), 127.30 (1C, t),
30.94 (1C, t), 131.93 (1C, t), 133.41 (1C, q), 135.44 (1C, q),
35.91 (1C, q), 138.24 (1C, q), 138.86 (1C, q), 141.09 (1C, q),
41.32 (1C, q), 168.29 (1C, q).
Soc. 1976, 98, 6119; L. I. Yeh, J. M. Price, Y. T. Lee, J. Am.
Chem. Soc. 1989, 111, 5597; J. W. de M. Carneiro, P. von R.
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East, Z. F. Liu, C. McCague, K. Cheng, J. S. Tse, J. Phys. Chem.
A 1998, 102, 10903.
X-ray Crystallography. Crystals of compounds 26, 30, 46,
and 54 were grown from diethyl ether–hexane. The crystal data
and the parameters for data collection, structure determina-
tion, and refinement are summarized in Table 1. Diffraction data
were collected on a Rigaku AFC7R or a Rigaku/MSC Mercury
CCD diffractometer and calculations were performed using the
SHELXL97 program.22 The structures were solved by direct
methods followed by full-matrix least-squares refinement with
all non-hydrogen atoms anisotropic and all hydrogen atoms iso-
tropic. Reflection data with jIj > 2:0ꢂðIÞ were used.
6
A part of the results has been reported in a preliminary
form: G. Yamamoto, H. Mochida, Chem. Lett. 2000, 454.
T. Kawase, N. Asai, T. Ogawa, M. Oda, J. Chem. Soc.,
Chem. Commun. 1990, 339.
7
8
Chem. 1965, 8, 342.
E. C. Kornfeld, P. Barney, J. Blankley, W. Faul, J. Med.
9
U. Berg, J. Sandstr o¨ m, Adv. Phys. Org. Chem. 1989, 25, 1.
10 See for example: J. E. Anderson, R. W. Franck, W. L.
Mandella, J. Am. Chem. Soc. 1972, 94, 4608; M. S. Newman,
R. Kannan, J. Org. Chem. 1976, 41, 3356; G. Yamamoto, M.
Crystallographic data have been deposited with Cambridge
Crystallographic Data Centre: Deposition numbers CCDC-
¯
Suzuki, M. Oki, Bull. Chem. Soc. Jpn. 1983, 56, 306; G.
¯
Yamamoto, M. Oki, Bull. Chem. Soc. Jpn. 1986, 59, 3597; G. W.
6
09632 to CCDC-509635 for compounds 26, 30, 46, and 54,
respectively. Copies of the data can be obtained free of charge
via http://www.ccdc.cam.ac.uk/conts/retrieving.html (or from the
Cambridge Crystallographic Data Centre, 12, Union Road, Cam-
bridge, CB2 1EZ, UK; Fax: +44 1223 336033; e-mail: deposit@
ccdc.cam.ac.uk).
Gribble, D. J. Keavy, S. E. Branz, W. J. Kelly, M. A. Pals,
Tetrahedron Lett. 1988, 29, 6227.
11 For the stereochemical descriptors for the conformational
isomers, see: W. Klyne, V. Prelog, Experientia 1960, 16, 521;
¯
M. Oki, Top. Stereochem. 1983, 14, 1; G. Yamamoto, C. Agawa,
T. Ohno, M. Minoura, Y. Mazaki, Bull. Chem. Soc. Jpn. 2003, 76,
1
801.
1
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M. Oki, Y. Taguchi, T. Miyasaka, M. Kitano, S. Toyota, T.
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