Iodination of tricyclo[4.1.0.02,7]heptane in the presence of external nucleophiles

Article abstract of DOI:10.1023/A:1020382903063

Tricyclo[4.1.0.0^2,7]heptane reacted with iodine, N-iodosuccinimide, and iodine monochloride in the presence of external nucleophiles yielding products of conjugate endo,syn addition at the central C¹-C⁷ bond. The mechanism

Full text of DOI:10.1023/A:1020382903063

Russian Journal of Organic Chemistry, Vol. 38, No. 6, 2002, pp. 803 809. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 6, 2002,
pp. 845 851.
Original Russian Text Copyright
2002 by Vasin, Semenov, Razin.
2,7
Iodination of Tricyclo[4.1.0.0 ]heptane in the Presence
of External Nucleophiles*
V. A. Vasin1, A. V. Semenov1, and V. V. Razin2
1Ogarev Mordovian State University, Saransk, 430000 Russia
2St. Petersburg State University, St. Petersburg, Russia
Received December 5, 2001
Abstract Tricyclo[4.1.0.02,7]heptane reacted with iodine, N-iodosuccinimide, and iodine monochloride in
the presence of external nucleophiles yielding products of conjugate endo,syn addition at the central C1 C7
bond. The mechanism of these chemo- and stereoselective reactions is discussed.
Among the most interesting reactions of tricyclo-
[4.1.0.02,7]heptane (I) its reaction with iodine result-
ing in endo,syn-6,7-diiodobicyclo[3.3.1]heptane (IIa)
[1] should be mentioned. Two reaction features call
for attention: chemoselectivity (addition exclusively
to the central C1 C7 bond) and strict stereospecificity:
cis-addition with reversal of configuration of both
carbon atoms of the central bond. Yet the most addi-
tion reactions with hydrocarbon I occur nonselective-
ly, either at the side bond C1 C2, or at the central
C1 C7 bond, as a rule nonselectively [2 5]. In studies
carried out with application of the ESR spectroscopy
[6, 7] with the use of 2,4,6-tribromonitrosobenzene
as a spin trap in the reaction under discussion, and in
the reaction of iodine with [1.1.1]propellane (III) a
formation of paramagnetic intermediates was revealed
that supported the previously assumed hypothesis [8]
they entered into adducts, and alongside iodide IIa
formed the products of conjugate addition IIb and
IIc.**
Similar reasoning was used in [11, 12] to assume
ionic mechanism with respect to iodination of
propellane (III).
In this study we carried out a supplementary
research on elemental iodine addition to hydrocarbon
I in the presence of external nucleophiles with con-
siderably wider range of these substances as com-
pared with [10]. We also performed iodination reac-
tions using as sources of electrophilic iodine N-iodo-
succinimide (NIS) and iodine monochloride. In the
most cases the reactions were carried out in DMF for
it sufficiently well solved and activated by specific
solvation the mineral salts used as a source of an
on the radical mechanism of addition to compound III. external anionoid nucleophile. We should note at
These results allowed extension of the hypothesis on
the radical reaction mechanism to compound I. This
assumption is well consistent with observed chemo-
selectivity of hydrocarbon I iodination since this
feature is characteristic of all the known radical
addition reactions to this hydrocarbon [3]. However
in contrast to the reaction under discussion the other
radical additions to compound I are not stereo-
selective: form endo,syn and endo,anti adducts with
the latter prevailing [9]. An important evidence for
alternative ionic mechanism of tricycloheptane I
iodination were results of an experiment carried out
in dissertation of J. Morf [10] performed under the
guidance of Professor G. Szeimies: in the presence of
external nucleophiles (bromide and chloride ions)
once, that virtually in all reactions performed in this
solvent a formation of formate IId as a side product
was observed. Such involvement of DMF as a mild
O-nucleophile into the conjugate addition in reactions
of halofunctionalization of alkenes was reported
Nu = I (a), Br (b), Cl (c), O2CH (d), SCN (e), N3
(f), O2CMe (g), O2CPh (h), OMe (i), OH (j).
*
**
The study was carried out under financial support from the
The authors are grateful to Professor G. Szeimies for the
Russian Ministry of Education (grant no. E 00-5.0-30).
possibility to become acquainted with dissertation [10].
1070-4280/01/3806-803$27.00 2002 MAIK Nauka/Interperiodica

804
VASIN et al.
Table 1. Reaction conditions and yield of products from reactions of hydrocarbon I with iodinating reagents in the
presence of external nucleophiles
Reaction
no.
Reagents
I+ + Nu
I+ / Nu
(mol)
Reaction products
(composition, %)
Yield of the main
reaction product, %
Solvent
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
I2+KI
I2+LiBr
DMF
DMF
MfOH
CCl4
1: 5
1: 10
1: 5
1: 3
1: 10
1: 5
1: 10
1: 5
1: 5
IIa (91), IId (1), (8)a
IIa (9), IIb (90), IId (1)
IIa (18), IIb (82)
IIa (65)
IIb (74)
IIb (31)
IIc (11)
IIe (42)
IIf (20)
IIb (40)
I2+Et3BnNCl
I2+KSCN
I2+NaN3
IIa (35), IIc (65)
DMF
DMF
DMF
DMF
CH2Cl2
CH2Cl2
DMF
DMF
MeOH
Acetone
DMF
DMF
IIa (40), IId (12), IIe (48)
IIa (44), IId (4), IIf (52)
IIb (97), IId (3)
NIS+LiBr
NIS+NaN3
NIS+AcOHb
NIS+PhCO2Hb
NIS+DMF
NIS+HCO2Na
NIS+MeOH
NIS+H2Ob
ICl+LiCl
IIa (13), IId (14), IIf (68), (5)a IIf (22)
IIg (90), (10)a
IIg (56)
IIh (30)
IId (67)
IId (34)
IIi (48)
IIj (9), IV+V (40)
IIc (46)
VIa+VIIa (47)
VIb+VIIb (32)
1: 5
IIh (>85)
1: 39
1: 10
1: 74
1: 56
1: 10
1: 2
IIa (12), IId (84), (4)a
IIa (49), IId (50), (1)a
IIi (82), (18)a
IIj (14), IV (65), V (21)
IIc (86), II (4), (10)a
VIa (28), VIIa (72)
VIb (46), VIIb (54)
NIS+PhSO2Na
NIS+p-MeC6H4SO2Hb CH2Cl2
1: 2
a
b
Unidentified impurities. With addition of equimolar amount of triethylamine, see EXPERIMENTAL.
formerly in [13]. The data on composition of products
obtained in reactions (1 15) of compound I initiated
by electrophilic iodine in the presence of external
nucleophile are presented in Table 1.
of diiodide IIa as an impurity in products of reactions
with NIS (8, 11, 12) is apparently due to the partial
reduction of the latter to I2 either by solvent (DMF)
or anionoid nucleophile. The reaction between hydro-
carbon I and NIS in methanol (reaction 13) resulted
in iodomethoxylation product IIi that failed to form
in reaction with elemental iodine (reaction 3). In
reaction (14) with NIS in aqueous acetone in the
presence of triethylamine was revealed a formation of
norpinane iodohydrin IIj, but the main products of
this reaction were two stereoisomers IV and V
resulting from iodohydroxylation of compound I at
the side bond C1 C2.
In reactions (2, 4 6) with elemental iodine in DMF
in the presence of lithium bromide, potassium thio-
cyanate, or sodium azide, and also in CCl4 in the
presence of triethylbenzylammonium chloride
(Et3BzNCl) compounds IIb, c, e, f resulting from
conjugate were obtained addition as main products.
A similar result (formation of a mixed haloderivative
IIb) was observed also in reaction (3) of compound I
with I2 in methanol in the presence of lithium
bromide, but methanol did not participate in the con-
jugate addition.
The fraction of products of conjugate addition
arising in reactions with NIS in the presence of
sodium azide or lithium bromide in DMF (reactions
7, 8) was a little larger that in mixture treated with
I2. With NIS were also prepared acetate IIg and
benzoate IIh by carrying out the reaction in dichloro-
methane in the presence of excess corresponding
acids and triethylamine (reactions 9, 10). Formate IId
is the main product of reaction between hydrocarbon
I and NIS in DMF (reaction 11). The yield of com-
pound IId did not grow on addition to the reaction
mixture of sodium formate (reaction 12). Appearance
The use as iodinating agent of iodine monochloride
with lithium chloride as additive in DMF (reaction
15) both increased the fraction of the product of
conjugate addition IIc in the reaction mixture and
considerably increased its yield as compared to reac-
tion (4).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

Table 2. Constants and elemental analyses of bicycloheptanes IIa j, VIa, b, VIIa, b
mp,
C
GLC analysis
Found , %
Caltd.,
C
%
Compd
(solvent or
Compound name
R
Formula
f
no.
Column R ,
crystallization), or
bp, C (mm Hg)
t
C
H
H
temp., C min
IIa
IIb
IIc
endo-6-syn-7-Diiodobicyclo[3.1.1]heptane
syn-7-Bromo-endo-6-iodobicyclo[3.1.1]heptane
endo-6-Iodo-syn-7-chlorobicyclo[3.1.1]heptane
120 121
(hexane)a
62 64b
0.68
0.77
0.78
150
150
150
12.3 24.51 3.03 C7H10I2
24.16 2.90
7.1 28.03 3.52 C7H10BrI 27.94 3.35
4.7 32.65 4.03 C7H10ClI 32.78 3.93
(hexane)
24 25c
(hexane)
IId
IIe
endo-6-Iodo-syn-7-formoxybicyclo[3.1.1]heptane
endo-6-Iodo-syn-7-thiocyanobicyclo[3.1.1]heptane
48 49 (2)
60 61
0.70
0.38
150
150
7.4 35.89 4.13 C8H11IO2 36.11 4.17
4.2 34.33 3.56 C8H10INS 34.42 3.61
(ether)
IIf
IIg
syn-7-Azido-endo-6-iodobicyclo[3.1.1]heptane
syn-7-Acetoxy-endo-6-iodobicyclo[3.1.1]heptane
66 68 (20)
Oily
0.68
0.58
150
150
6.0 32.10 3.91 C7H10IN3 31.96 3.83
8.0 38.66 4.82 C9H13IO2 38.59 4.68
substance
83 84
(ether)
Oily
substance
81 82
IIh
IIi
syn-7-Benzoyloxy-endo-6-iodobicyclo[3.1.1]heptane
endo-7-iodo-syn-7-methoxybicyclo[3.1.1]heptane
syn-7-Hydroxy-endo-6-iodobicyclo[3.1.1]heptane
endo-6-iodo-syn-7-phenylsulfonylbicyclo[3.1.1]heptane
0.69
0.60
0.27
0.37
0.27
0.48
0.33
49.21 4.47 C14H15IO2 49.14 4.42
130
140
8.1 38.32 5.29 C8H13IO
15.0 35.48 4.74 C7H11IO
38.12 5.20
35.32 4.66
IIj
(ether)
127 128
VIa
220d
220d
220d
220d
10.5 43.02 4.12 C13H15IO2S 43.10 4.17
14.7 44.45 4.65 C14H17IO2S 44.69 4.55
6.0 43.09 4.24 C13H15IO2S 43.10 4.17
9.6 44.55 4.36 C14H17IO2S 44.69 4.55
(hexane chloroform)
167 168
VIb endo-6-iodo-syn-7-n-tolylsulfonylbicyclo[3.1.1]heptane
VIIa exo-6-iodo-syn-7-phenylsulfonylbicyclo[3.1.1]heptane
VIIb exo-6-iodo-syn-7-n-tolylsulfonylbicyclo[3.1.1]heptane
(hexane chloroform)e
142 143
(hexane chloroform)
147 148
(hexane chloroform)e
b
c
d
a mp 120 121 C (from methanol) [1]. bp 72 80 C (0.1 mm Hg) [10]. bp 40 50 C (0.1 mm Hg) [10]. Column 1.5 m long. e In agreement with published data [9].

806
VASIN et al.
1
Table 3. H NMR spectra of bicycloheptanes IIa j, VIa, VIIa, , ppm
2,4
eq
2,4
ax
Compd.
no.
H6
H7
H1,5
H
H
H3
Other signals
IIa
IIb
IIc
IId
IIe
IIf
IIg
IIh
IIi
4.53 t
2.74a
2.80
2.79
2.86
2.85
2.74
2.82
2.96
2.75
2.67
2.75
2.73
2.08 2.23
1.60 1.75
1.52 1.80
1.50 1.77
1.49 1.73
1.42 1.90
1.51 1.75
1.47 1.61
1.56 1.80
1.54 1.72
1.45 1.77
4.45 t
4.35 t
4.26 t
4.51 t
4.32 t
4.25 t
4.35 t
4.20 t
4.19 t
4.38 t
4.01 s
4.35 tb
4.30 tb
4.96 t
4.07 t
4.05 t
4.83 t
5.12 t
3.71 t
4.17 t
3.45 t
4.14 t
2.12 2.36
2.15 2.35
2.00 2.15
1.95 2.23
2.05 2.25
1.95 2.15
2.08 2.25
1.98 2.15
2.05 2.25
2.33 2.60
2.44 2.64
1.85 2.12
1.90 2.10
1.85 2.00
1.70 1.95
1.76 2.00
1.82 1.95
1.90 2.05
1.76 1.95
1.82 1.98
8.12 s (CH=O)
2.10 s (Me)
7.5 t, 7.6 t, 8.1 d
3.37 s (OMe)
IIj
VIa
VIIa
2.18 s (OH)
7.40 7.52 (3H), 7.74 7.86 (2H)
7.43 7.62 (3H), 7.76 7.85 (2H)
1.62 2.03
1.65 2.13
b
a All signals of H1,5 are narrow multiplets. Assignment of signals of H6 and H7 for compounds IIb and IIc may be interchanged.
Table 4. 13C NMR spectra of bicycloheptanes IIa j, VIa, VIIa, , ppm
Compd.
no.
C6
C7
C1,5
C2,4
C3
Other signals
IIa
IIb
IIc
IId
IIe
IIf
IIg
IIh
IIi
18.9
47.0
47.0
46.9
44.8
45.1
45.0
44.7
45.0
44.8
46.4
44.8
49.0
28.8
26.8
25.4
25.2
25.1
25.1
25.3
25.5
25.0
24.4
24.0
24.6
9.9
10.7
11.0
11.9
10.9
11.6
12.1
12.2
12.5
12.0
11.9
13.0
22.4
24.0
25.8
25.7
28.8
26.7
26.6
28.2
26.9
28.1
24.7
42.2
51.0
66.1
42.9
55.2
66.2
66.6
72.9
65.0
58.7
60.5
160.0 (C=O)
111.50 (SCN)
20.7 (Me), 170.1 (C=O)
128.4, 129.5, 129.7, 131.1 (C arom), 165.5 (C=O)
56.4 (OMe)
IIj
VIa
VIIa
127.2, 129.2, 133.5, 139.9 (C arom)
127.2, 129.2, 133.4, 140.0 (C arom)
It should be noted that the yield of diiodide IIa
in reaction (1) of tricycloheptane I with elemental
iodine significantly increased in the presence of
external nucleophile as compared to the reaction
carried out without this additive. This fact is in
agreement with conclusion made in [10]. It was also
established that in the absence of external nucleo-
philes reaction between hydrocarbon I and iodine
monochloride or NIS in CH2Cl2 (cf. [14]) did not
provide the corresponding addition products and
yielded only unidentified polymeric substances.
elemental analyses of the compounds are given in
Table 2. Diiodide IIa and iodohalides IIb and IIc
were identified by comparison of their constants and
spectral characteristics with the published data [1, 10,
15]. The norpinane structure and configuration of
compounds IId j is reliably established from the
1
analysis of their H and 13C NMR spectra that are
consistent with those of norpinanes IIa c (see
Table 3; also cf. [16]).
The structure of norcarane endo,endo-adduct IV
was established from the expected similarity of its
1H and 13C NMR spectra with those of a known
bromo analog [17]. The structure of compound V was
ascribed to the third product of reaction (14) detected
Norpinane adducts IIa j were isolated as in-
dividual compounds by flash-chromatography follow-
ed by crystallization or distillation. The constants and
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

IODINATION OF TRICYCLO[4.1.0.02,7]HEPTANE
807
by GLC but not isolated individually by analogy to
the results of reaction between hydrocarbon I and
N-bromosuccinimide in water-acetone mixture [17],
reason thereto is the fact of strict endo,syn-selectivity
of addition characteristic of reactions (1 15). To
rationalize this stereochemistry of addition a non-
classical carbocation A originating from an attack of
electrophilic iodine on the nonbonding orbital of the
nodal carbon atom in the central C1 C7 bond should
be assumed as an intermediate of the ionic reaction
(cf. [4, 5]). The nucleophilic attack on the C7 atom
of this cation should be strictly stereodirected and
should proceed with reversal of the configuration.
1
and proceeding from the H NMR spectrum of a
mixture of compounds IV and V. In the spectrum
appeared a multiplet signal at 3.90 ppm characteristic
of H2 proton of endo,endo-adduct V (cf. with spectral
data for its bromo analog [17]).
Thus the reaction of hydrocarbon I with sources of
electrophilic iodine (I2, NIS, ICl) in the presence of
external nucleophiles proceeds as conjugate endo,syn-
addition to the central C1 C7 bond, i.e. it is char-
acterized by the same chemo- and stereoselectivity as
the standard reaction of compound I with elemental
iodine. Our additional experimental data (compared to
[10]) on the products of conjugate addition seem to
support the conclusion of this study (also see [4]) on
the ionic mechanism of the reaction in question. Yet
the fact proper of formation of the conjugate addition
products is not an unambiguous proof of this mechan-
ism. Actually published data exist describing the
possibility of NuI formation by preliminary reaction
of the electrophilic iodine with the external nucleo-
phile, and these compounds may further react with
substrate by radical mechanism. For instance, this
concept was applied to conjugate addition mechanism
in reaction of elemental iodine with alkenes in the
presence of NaN3 and ArSO2Na (with participation
of IN3 and ArSO2I formed in situ) [18, 19]. Just this
case occurred in our experiment when hydrocarbon I
reacted with NIS in the presence as external nucleo-
philes of sodium benzenesulfinate or p-toluenesulfinic
acid (with triethylamine added) (reactions 16 and 17).
Here in contrast to previously considered reactions
(1 15) alongside the corresponding endo,syn-adduct
VIa, b formed its stereoisomer exo,syn-adduct
VIIa, b in commensurable quantity. The formation
of compound VII can be understood only from the
viewpoint of radical mechanism as was confirmed
with a direct experiment: a reaction of hydrocarbon I
with ArSO2I (see also [9]).
The higher stability of cation A compared with
analogous carbocation generated by electrophilic
attack of a proton on the same substrate is due as we
believe to the presence of a iodine atom in the endo-
position 6. The cation arising from attack of a proton
is known [20] to suffer a fast isomerization into more
stable 2-norcaranyl cation. The stabilization of cation
A by iodine atom is due to homohyperconjugation
effect as has been previously presumed [21] for a
related cation B, an intermediate in propellane III
iodination (see also [22]).
A specific behavior of hydrocarbon I in reaction
with NIS in an aqueous acetone (reaction 14) as
compared with the other reactions (1 13) may be also
rationalized within the framework of the ionic
mechanism: primarily formed carbocation A in the
medium of high dielectric permittivity suffers stereo-
directional isomerization into carbocation C (2-nor-
caranyl one), see [5], that is a precursor of norcaranes
IV and V.
EXPERIMENTAL
1H and 13C NMR spectra were registered on
spectrometer Bruker AC-300 at operating frequencies
300.130 and 75.469 MHz respectively from solutions
in CDCl3. The spectra of norpinanes IIa j, VIa, and
VIIa are presented in Tables 3 and 4. GLC analyses
were carried out on cromatograph Chrom-4 equipped
with flame-ionization detector, glass column 3500
3 mm, stationary phase 3% OV-17 on Inerton
N-Super (0.125 0.160 mm), carrier gas nitrogen,
Ar = Ph (a), p-Tol (b).
1
Thus for reactions (16, 17) we assume radical
mechanism of conjugate addition, yet in the other
cases we favor the ionic mechanism, and the key
flow rate 40 ml min . Analytical TLC was perform-
ed on Silufol UV-254 plates, eluent hexane ether,
1: 1, development in iodine vapor. Flash-chromato-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

808
VASIN et al.
Reaction of hydrocarbon I with elemental iodine
graphy was performed on silica gel L 40/100
eluent light petroleum ether ethyl ether, 3: 1.
,
in methanol in the presence of LiBr. To a solution
of 0.94 g of tricycloheptane I in 10 ml of anhydrous
methanol containing 4.35 g of lithium bromide at stir-
ring under nitrogen atmosphere was added dropwise
while cooling to 0 C 2.54 g of iodine in 5 ml of
anhydrous methanol. The reaction mixture was stirred
for 1 h at room temperature, and then diluted with
20 ml of water. The reaction products were extracted
into chloroform. We obtained 1.54 g of a mixture of
halides IIa and IIb in 18: 82 ratio (according to the
Tricycloheptane (I), bp 109 110 C was synthesiz-
ed as described before [23]; its purity according to
GLC (30 C) attained 97%. Benzenesulfonyl iodide
and N-iodosuccinimide were prepared by known
procedures [24, 25].
Reaction of hydrocarbon I with iodinating
reagents (I2, NIS, ICl) in DMF in the presence of
external nucleophiles. General procedure. To a mix-
ture of 0.1 mol of an appropriate salt (KI, LiBr, LiCl,
KSCN, NaN3, HCOONa or PhSO2Na [26], see
Table 1), in 35 ml of DMF, and 0.01 mol of hydro-
carbon I in 5 ml of the same solvent at cooling with
ice bath was added dropwise under argon atmosphere
within 30 min 0.01 mol of iodinating reagent in 20 ml
of DMF. The reaction mixture was stirred at cooling
for 1.5 h, and then for 1.5 2 h more at 20 C. Then it
was diluted with water, reaction products were
extracted with ether (3 30 ml), extract was treated
with 5% water solution of Na2SO3 till disappearance
of iodine color, washed with water, and dried with
sodium sulfate. The solvent was removed in a
vacuum, and the semicrystalline mixture obtained was
1
data of GLC and H NMR), Table 1.
Reaction of hydrocarbon I with NIS in the
presence of acetic, benzoic, and p-toluenesulfinic
acids. General procedure. To a mixture of 50mmol
of anhydrous triethylamine and 50 mmol of acetic,
benzoic, or p-toluenesulfinic acid [27] in 30 ml of
anhydrous dichloromethane was added 0.94
g
(10 mmol) of tricycloheptane I. Then at stirring under
argon atmosphere and external cooling with an ice
bath 2.25 g (10 mmol) of NIS was added by small
portions. The stirring was continued for 1.5 h at 0 C
and for 2 h at room temperature. The mixture was
diluted with water, the organic layer was separated,
from the water layer the products were extracted with
CH2Cl2 (3 10 ml). The combined organic solu-
tions were dried on MgSO4. On removing the solvent
in a vacuum the residue was purified by flash-
chromatography. Yields of compounds IIg, h and
their constants are given in Tables 1 and 2. The con-
stants and spectral characteristics of compounds IVb
and VIIb were consistent with the published data [9].
1
analyzed by GLC and H NMR. The compositions of
the reaction mixtures are listed in Table 1. The main
reaction products were isolated by flash-chromato-
graphy and/or fractional crystallization. The constants
of bicycloheptanes IIa f, VIa, b, VIIa, b are given
in Table 2.
Reaction of hydrocarbon I with NIS in DMF.
The reaction of 10 mmol of tricyclohexane I with
10mmol NIS in DMF was performed as described
above in the general procedure save with no anionoid
nucleophile. The composition of the reaction mixture
and yield of compound IId isolated by vacuum
distillation are reported in Table 1.
Reaction of hydrocarbon
I with NIS in
methanol. To a solution of 0.94 g of hydrocarbon I
in 30 ml of anhydrous methanol at external cooling
to 0 C was added while stirring by portions within
1 h 2.15 g of NIS. The reaction mixture was diluted
with water, the reaction products were extracted
with ether, the extracts were dried on MgSO4, and
evaporated. The colorless oily substance obtained was
purified by flash-chromatography to obtain 1.2 g
(48%) of compound IIi.
Reaction of hydrocarbon I with elemental iodine
in CCl4 in the presence of Et3BzNCl. To a solution
of 0.94 g of compound I in 40 ml of anhydrous CCl4
was added 6.53 g of Et3BzNCl, and at stirring under
nitrogen atmosphere was added dropwise while cool-
ing to 0 C a solution of 2.54 g of I2 in 20 ml of CCl4.
The mixture was stirred for 0.5 h more at cooling and
for 1 h at 20 C, then it was diluted with water. The
organic layer was separated, and from the water layer
the products were extracted into CCl4 (3 10 ml).
The combined organic solvents were washed with 5%
water solution of Na2SO3, with water, and then dried
with MgSO4. On evaporating the extract in a vacuum
we obtained 1.3 g of crystalline compound composed
according to GLC data of a mixture of halides IIa and
IIc, Table 1.
Reaction of hydrocarbon I with NIS in aqueous
acetone. Into a mixture composed of 0.94 g of hydro-
carbon I, 20 ml of acetone, 10 ml of water, and 2 ml
of triethylamine cooled to 0 C was added within 0.5 h
2.15 g of NIS. The mixture was stirred at this
temperature for 0.5 h more, and then for 1.5 h at
20 C. The workup was carried out as described above.
The reaction products were divided by chromato-
graphy on silica gel in two fractions. The first one,
Rf 0.27, contained norpinane IIj, yield 23%. The
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002

IODINATION OF TRICYCLO[4.1.0.02,7]HEPTANE
809
second fraction, Rf 0.15, according to GLC data
(140 C) contained two compounds in 3: 1 ratio with
Rt 10.5 and 9.6 min respectively. They were
identified as endo-7-iodobicyclo[4.1.0]heptan-endo-6-
ol (IV) and endo-7-iodobicyclo[4.1.0]heptan-exo-6-ol
(V). The overall yield of compounds IV and V was
0.96 g (40%). The main component of the mixture,
compound IV, was isolated in an individual state by
crystallization, mp 71 72 C (from petroleum ether
Zh. Org. Khim., 1990, vol. 26, no. 7, pp. 1377 1383.
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pp. 680 685.
10. Morf, J., Dissertation. Univ. Munchen, 1988.
11. Wiberg, K.B. and McMurdie, N., J. Am. Chem. Soc.,
1994, vol. 116, no. 28, pp. 11990 11998.
12. Milne, I.R. and Taylor, D.K., J. Org. Chem., 1998,
vol. 63, no. 11, pp. 3769 3771.
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Asensio, G., Tetrahedron Lett., 1986, vol. 27, no. 15,
pp. 1715 1718.
14. Vasin, V.A., Bolusheva, I.Yu., Kostryukov, S.G.,
Sanaeva, E.P., Ramzevich, A.A., and Razin, V.V.,
Zh. Org. Khim., 1996, vol. 32, no. 5, pp. 698 704.
15. Vasin, V.A. Bolusheva, I.Yu., Surmina, L.S., Bue-
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1
ethyl ether, 3: 1). H NMR spectrum, , ppm: 1.10
1.50 m (3H); 1.55 1.70 m (3H); 1.80 m (1H); 1.95 d
(OH, J 9 Hz); 2.20 m (1H); 3.05 t (H7, J 8 Hz);
4.35 m (H2). 13C NMR spectrum, , ppm: 3.5 (C7);
17.3, 18.0, 22.7 (2C); 30.3, 69.0 (C2). Found, %:
C 35.49; H 4.64. C7H11IO. Calculated, %: C 35.32;
H 4.66.
1
In the H NMR spectrum of the residue obtained
by removal of solvent from the mother liquor a
multiplet signal was observed at 3.90 ppm character-
istic of the H2 proton in endo,endo adduct V (cf. with
the spectral data of the bromo analog of compound V
[17]).
Reaction of hydrocarbon I with benzenesulfonyl
iodide. At external cooling with ice water solutions
in 5 ml of anhydrous $CH2Cl2 of 0.94 g of tricyclo-
heptane I and 2.68 g of PhSO2I were mixed. The
mixture was kept at 20 C under nitrogen for 20 h,
and then the solvent was removed in a vacuum of
water-jet pump. The solid residue containing accord-
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vol. 31, no. 7, pp. 2250 2254.
17. Gerstner, E., Kemmer, R., and Christl, M., Chem.
Ber., 1994, vol. 127, no. 2, pp. 381 391.
18. Najera, C., Baldo, D., and Yus M., J. Chem. Soc.
Perkin Trans. I, 1988, pp. 1029 1032.
19. Cambie, R.C., Jurlina, J.L., Rutledge, P.S., and
Woodgate, P.D., J. Chem. Soc. Perkin Trans. I,
1982, pp. 315 326.
1
ing to GLC and H NMR data a mixture of com-
pounds VIa and VIIa in 1: 1 ratio was subjected to
column chromatography on alumina. We obtained
respectively 1.61 and 1.32 g (45 and 36.5%) of
individual compounds with the constants listed in
Table 2.
20. Wiberg, K.B. and Szeimies, G., J. Am. Chem. Soc.,
1970, vol. 92, no. 3, pp. 571 579.
21. Della, E.W. and Janowski, W.K., Chem. Commun.,
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Elsey, G.M., Aust. J. Chem., 1995, vol. 48, no. 5,
pp. 967 985.
22. Levin, M.D., Kaszynski, P., and Michl, J., Chem.
Rev., 2000, vol. 100, pp. 169 234.
23. Razin, V.V., Eremenko, M.V., and Ogloblin, K.A.,
Zh. Org. Khim., 1978, vol. 14, no. 5, pp. 973 979.
24. Truce, W.E., Heuring, D.L., and Wolf, G.C., J.
Org. Chem., 1974, vol. 39, no. 2, pp. 238 244.
25. Fizer, L. and Fizer, M., Reagenty dlya organiche-
skogo sinteza (Reagents for Organic Cynthesis),
Moscow: Mir, 1970, vol. 2, p. 60.
26. Bordwell, F.G., Hout, E.B., Jarvis, B.B., and
Williams, J.M., J. Org. Chem., 1968, vol. 33, no. 5,
pp. 2030 2035.
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