Reaction of Tricyclo[4.1.0.02,7]heptane with 1-(Arenesulfonyl)-2-phenyldiazenes

Article abstract of DOI:10.1134/S107042802004003X

Abstract: Tricyclo[4.1.0.0^2,7]heptane reacted with1-(arenesulfonyl)-2-phenyldiazenes by radical mechanism to givebicyclo[3.1.1]heptane derivatives. Unlike analogous reactions with alkenes, theaddition of diazenes occurs readily without a catalyst and yields mainlyarylazosulfonation products at theC¹–C⁷ bond oftricyclo-[4.1.0.0^2,7]heptane. The additionproducts are capable of undergoing thermal prototropic isomerization to7-endo-(arenesulfonyl)bicyclo[3.1.1]heptan-6-onephenylhydrazones.

Full text of DOI:10.1134/S107042802004003X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2020, Vol. 56, No. 4, pp. 576–581. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Organicheskoi Khimii, 2020, Vol. 56, No. 4, pp. 522–529.
Reaction of Tricyclo[4.1.0.02,7]heptane
with 1-(Arenesulfonyl)-2-phenyldiazenes
S. G. Kostryukova,* and Yu. Yu. Masterovaa
a Ogarev Mordovian State National Research University, Saransk, 430005 Russia
*e-mail: kostryukov_sg@mail.ru
Received December 28, 2019; revised February 12, 2020; accepted February 13, 2020
Abstract—Tricyclo[4.1.0.02,7]heptane reacted with 1-(arenesulfonyl)-2-phenyldiazenes by radical mechanism
to give bicyclo[3.1.1]heptane derivatives. Unlike analogous reactions with alkenes, the addition of diazenes
occurs readily without a catalyst and yields mainly arylazosulfonation products at the C1–C7 bond of tricyclo-
[4.1.0.02,7]heptane. The addition products are capable of undergoing thermal prototropic isomerization to
7-endo-(arenesulfonyl)bicyclo[3.1.1]heptan-6-one phenylhydrazones.
Keywords: 1-(arenesulfonyl)-2-phenyldiazenes, tricyclo[4.1.0.02,7]heptane, radical addition, bicyclo[3.1.1]-
heptane, prototropic rearrangement
DOI: 10.1134/S107042802004003X
1-(Arenesulfonyl)-2-phenyldiazenes are known
[1–3] to react with some alkenes in the presence of
Pd(PPh3)4 as catalyst to give mainly arylation and
arenesulfonation products. The major products in the
reactions with α,β-unsaturated esters are β-aryl-substi-
tuted alkenes, whereas α,β-unsaturated ketones under-
go both arylation and arenesulfonation [2]. However,
styrene under similar conditions gave rise to sulfonyl-
substituted azo compounds in addition to the arylation
products [3], whereas radical polymerization of styrene
was observed under photochemical and thermal initia-
tion [4]. It has also been found that arenesulfonyl and
aryl radicals are generated in the photochemical de-
composition of aryl aryldiazenyl sulfones [5]. The
synthesis of substituted allylarenes via photochemical
generation of aryl radicals from aryldiazenyl sulfones
and their subsequent reaction with allyl sulfones has
been reported [6].
sulfonyl)-2-phenyldiazene (2b) at 60–70°C in benzene
to give multicomponent mixtures of bicyclo[3.1.1]-
heptane derivatives 3–7 (Scheme 1). The compositions
of the reaction mixtures were determined by H NMR
spectroscopy. Compounds 3a and 3b were isolated in
1
the pure state by alumina column chromatography and
1
were characterized by IR, H and 13C NMR, and mass
spectra and elemental analyses. The other components
(compounds 4a, 4b, 5a, 5b, 6a, 6b, 7a, and 7b) were
identified in the reaction mixtures without isolation by
comparing with authentic samples which were prepared
by independent syntheses. In particular, sulfones 4a
and 4b were synthesized by peroxide oxidation of the
corresponding arenethiol–1-phenyltricyclo[4.1.0.02,7]-
heptane (8) adducts [8], and sulfones 5a and 5b were
prepared in a similar way from tricycloheptane 1 [9].
In the case of compound 8, we obtained mixtures of
stereoisomeric sulfones 4a/9a and 4b/9b at a ratio of
~1:5.5 (Scheme 2); the pure stereoisomers were isolat-
ed by alumina column chromatography.
In recent years, 1-aryl-2-(methanesulfonyl)diazenes
have been used in the photochemical arylation of
diarylethenes [7]. Taking into account some structural
similarity between the π-bond of alkenes and central
C–C bond of bicyclo[1.1.0]butanes, we presumed that
1-(arenesulfonyl)-2-phenyldiazenes could also react
with the latter. We selected one of the most accessible
hydrocarbons of the bicyclo[1.1.0]butane series, tri-
cyclo[4.1.0.02,7]heptane (1), as a model compound.
Phenylhydrazones 6a and 6b were synthesized from
ketones 7a and 7b which were prepared in turn by
addition of the corresponding arenesulfonyl bromides
to 1-(phenylsulfanyl)tricyclo[4.1.0.02,7]heptane (10),
followed by hydrolysis (Scheme 3), according to [10];
4-methylbenzenesulfonyl derivative 7b and its phenyl-
hydrazone 6b were not reported previously.
In fact, compound 1 reacted with 1-(benzenesul-
fonyl)-2-phenyldiazene (2a) and 1-(4-methylbenzene-
The bicyclo[3.1.1]heptane structure of 3–7 is con-
firmed by the presence of 5 peaks in their 13C NMR
576

REACTION OF TRICYCLO[4.1.0.02,7]HEPTANE
577
Scheme 1.
3
4
5
2
1
Δ
SO2Ar
SO2Ar
N
SO2Ar
+
+
6
Ph
N
7
Ph
N
Ph
N
1
2a, 2b
3a (50%), 3b (47%)
4a (22%), 4b (20%)
+
+
+
SO2Ar
SO2Ar
SO2Ar
N
O
NH
Ph
5a (8%), 5b (10%)
6a (15%), 6b (18%)
7a (5%), 7b (5%)
Ar = Ph (a), 4-MeC6H4 (b).
spectra with proper intensities and chemical shifts. The
orientation of substituents in molecules 3–7 was in-
ferred from the analysis of the positions and multi-
which pure compounds 3a and 3b in benzene were
heated at 60–70°C for 10 h; according to the H NMR
data, the conversion of 3a and 3b into hydrazones 6a
and 6b was 35–40%.
1
1
plicities of the 6-H and 7-H signals in the H NMR
spectra with account taken of known correlations
[8–10]. The triplet signal of 7-H indicated anti orienta-
tion of that proton with respect to the trimethylene
bridge. Likewise, the singlet signal of 6-H in the spec-
tra of 3a, 3b, 4a, and 4b corresponds to its syn orienta-
tion. The diazenyl fragment gave rise to an IR band at
1477 cm–1, and the sulfonyl group characteristically
showed stretching vibration bands at ~1145 and
~1310 cm–1. Compounds 6a and 6b were formed as
a result of thermal prototropic rearrangement of azo
isomers 3a and 3b. The occurrence of this isomeriza-
tion was confirmed by independent experiment in
The formation of ketones 7a and 7b may be
rationalized assuming concurrent thermally induced
prototropic rearrangement of 3a and 3b into phenyl-
hydrazones 6a and 6b and hydrolysis of the latter with
traces of water present in the reaction mixture. This
was confirmed by the intentional transformation of
bicycloheptanes 3a and 3b to ketones 7a and 7b on
heating at 50–55°C for 4 h in aqueous tetrahydrofuran
(Scheme 4). The pure products were isolated by crys-
tallization, and the structure of 7b was assigned on the
1
basis of its IR and H and 13C NMR spectra and the
corresponding data for known analog 7a [10].
Scheme 2.
(1) ArSH
(2) AcOOH
+
SO2Ar
R
SO2Ar
R
R
1, 8
4a, 4b
5a, 5b, 9a, 9b
1, 5, R = H; 4, 8, 9, R = Ph; Ar = Ph (a), 4-MeC6H4 (b).
Scheme 3.
(1) ArSO2Br
(2) H2O
PhNHNH2
SO2Ar
SO2Ar
PhS
O
N
NH
Ph
10
7a, 7b
6a, 6b
Ar = Ph (a), 4-MeC6H4 (b).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 4 2020

KOSTRYUKOV, MASTEROVA
578
Scheme 4.
PhH, Δ
H2O/THF, Δ
SO2Ar
SO2Ar
SO2Ar
N
O
Ph
N
N
NH
Ph
6a, 6b
3a, 3b
7a, 7b
Ar = Ph (a), 4-MeC6H4 (b).
Thus, the major products in the reactions of 1 with
azo sulfones 2a and 2b are 1:1 adducts where the azo
fragment is retained; this is somewhat surprising in
comparison with analogous alkene reactions. We
believe that bicyclo[3.1.1]heptanes 3–5 are formed via
a homolytic pathway (Scheme 5) starting from dis-
sociation of the N–S bond in the reagent. Next follows
endo attack of the liberated sulfonyl radical to the
bridgehead carbon atom of tricycloheptane 1. Inter-
mediate bicycloheptyl radical A adds to azo sulfone 2
to give hydrazinyl radical B, and elimination of arene-
sulfonyl radical from B yields product 3. Compound 4
is formed as a result of coupling of radical A and
phenyl radical generated by loss of nitrogen from
phenyldiazenyl radical. Small amounts of compounds
5 can appear in the reaction mixtures via abstraction
of hydrogen from the solvent by radical A, as reported
in [9] for the addition of sulfonyl chlorides to
tricycloheptane 1.
In summary, 1-(arenesulfonyl)-2-phenyldiazenes 2a
and 2b react with tricyclo[4.1.0.02,7]heptane (1) to
afford 6-(arenesulfonyl)-7-(phenyldiazenyl)bicyclo-
[3.1.0]heptanes as the major products. The addition
reaction features the same regio- and stereoselectivity
as in other sulfonation reactions of compound 1, e.g.,
with sulfonyl halides [9], sulfonothioic and sulfono-
selenoic acid esters [11], and ethynyl [12] and allyl
sulfones [13].
EXPERIMENTAL
1
The H and 13C NMR spectra were recorded from
solutions in CDCl3 on a Jeol JNM-ECX400 spectrom-
eter (Japan) at 400 and 100 MHz, respectively, using
the residual proton (δ 7.26 ppm) and carbon signals
(δC 77.16 ppm) of the solvent as reference. The IR
spectra were recorded in KBr on an InfraLYuM FT-02
spectrometer (Lyumeks Ltd., Russia). Elemental anal-
Scheme 5.
1
·
Ph
N
4a, 4b
–N2
·
Ph
Δ
·
·
+
SO2Ar
Ph
N
2a, 2b
ArSO2
SolvH
·
A
5a, 5b
3a, 3b
2a, 2b
ArSO2
N
·
ArSO2
N
Ph
B
Ar = Ph (a), 4-MeC6H4 (b).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 4 2020

REACTION OF TRICYCLO[4.1.0.02,7]HEPTANE
579
ysis was carried out with an Elementar Vario MICRO
CHNS analyzer (Germany). Analytical TLC was per-
formed on Silufol UV-245 plates using light petroleum
ether–ethyl acetate (4:1) as eluent; spots were visual-
ized by treatment with iodine vapor or under UV light.
Aluminum oxide (Brockmann activity grade II, 0.04–
0.2 mm, KhromLab Ltd.) was used for column chro-
matography; eluent light petroleum ether–ethyl acetate,
6:1 to 3:1. The melting points were measured in sealed
glass capillary tubes using a Mettler-Toledo MP-50
melting point analyzer (Switzerland). The mass spectra
(electron impact, 70 eV) were obtained on a KONIK
RBK-HRGC 5000B-MSQ12 instrument (Konixbert
Hi-Tech, Spain).
44.2 (C1, C5), 60.4 (C7), 79.5 (C6), 122.2 (2C, Carom),
127.5 (2C, Carom), 129.0 (2C, Carom), 129.3 (2C, Carom),
130.8 (Carom), 133.4 (Carom), 140.5 (Carom), 151.7
(Carom). Mass spectrum, m/z (Irel, %): 340 (2) [M]+, 235
(20), 199 (33), 142 (68), 105 (68), 93 (100). Found, %:
C 67.09; H 5.88; N 8.29. C19H20N2O2S. Calculated, %:
C 67.03; H 5.92; N 8.23.
6-syn-(4-Methylbenzenesulfonyl)-7-exo-(phenyl-
diazenyl)bicyclo[3.1.1]heptane (3b). Yield 200 mg
(21%), yellow–orange crystals, mp 159–161°C
(decomp., from acetone–petroleum ether). IR spectrum,
ν, cm–1: 2955 w, 1477 w (N=N), 1448 w, 1311 s (SO2,
asym.), 1285 s, 1142 s (SO2, sym.), 1088 m, 818 m,
1
764 w, 671 v.s, 606 m. H NMR spectrum, δ, ppm:
1.86–1.97 m (1H, endo-3-H), 2.03–2.201 m (3H,
exo-3-H, endo-2-H, endo-4-H), 2.44 s (3H, CH3C6H4),
2.81–2.88 m (2H, exo-2-H, exo-4-H), 3.03 br.s (2H,
1-H, 5-H), 4.20 s (1H, endo-6-H), 4.58 t (1H, anti-7-H,
J = 5.9 Hz), 7.36 d (2H, Harom, J = 7.9 Hz), 7.42–
7.44 m (3H, Harom), 7.62–7.65 m (2H, Harom), 7.82 d
(2H, Harom, J = 8.2 Hz). 13C NMR spectrum, δC, ppm:
14.6 (C3), 21.6 (CH3C6H4), 23.3 (C2, C4), 44.2 (C1,
C5), 60.5 (C7), 79.5 (C6), 122.3 (2C, Carom), 127.6 (2C,
Phenylhydrazine hydrochloride (≥99%), benzene-
thiol (97%), and 4-methylbenzene-1-thiol (98%) were
commercial products (Sigma–Aldrich). The solvents
were distilled prior to use.
Tricyclo[4.1.0.02,7]heptane (1) [14], 1-phenyltri-
cyclo[4.1.0.02,7]heptane (8) [15], 1-(phenylsulfanyl)tri-
cyclo[4.1.0.02,7]heptane (9) [16], 1-(benzenesulfonyl)-
2-phenyldiazene (2a), 1-(4-methylbenzenesulfonyl)-2-
phenyldiazene (2b) [17], and compounds 4a, 9a [8],
5a, 5b [9], and 7a [10] were synthesized according to
reported procedures.
C
arom), 129.0 (2C, Carom), 130.0 (2C, Carom), 130.8
(Carom), 137.6 (Carom), 144.3 (Carom), 151.7 (Carom).
Mass spectrum, m/z (Irel, %): 300 (30) [M]+, 285 (25),
272 (33), 246 (34), 194 (100), 167 (40), 103 (40), 63
(50). Found, %: C 67.80; H 6.29; N 7.88. C20H22N2O2S.
Calculated, %: C 67.77; H 6.26; N 7.90.
Reaction of tricycloheptane 1 with 1-(arenesul-
fonyl)-2-phenyldiazenes 2a and 2b (general proce-
dure). A flat-bottom flask equipped with a magnetic
stirrer was charged with a solution of 0.51 g (5.4 mmol)
of tricycloheptane 1 in 12 mL of anhydrous benzene
and a solution of 2.7 mmol of 2a or 2b in 12 mL of
anhydrous benzene. The mixture was stirred at 60–
70°C for 14 h under dry argon. The solvent was
removed under reduced pressure, and the residue was
Independent synthesis of compounds 4b and 9b.
A solution of 1.70 g (10 mmol) of 1-phenyltricyclo-
heptane 8 in 12 mL of carbon tetrachloride was mixed
with a solution of 1.51 g (12 mmol) of 4-methylben-
zenethiol in 12 mL of carbon tetrachloride, and the
mixture was kept in a tightly capped flask at 20°C for
24 h. The mixture was washed with 10 mL of
5% aqueous sodium hydroxide to remove excess thiol,
dried over CaCl2, and evaporated under reduced pres-
sure. The residue was cooled to –10°C, and 10 mL of
acetic acid, 10 mL of acetic anhydride, and 5 mL of
30% aqueous hydrogen peroxide were added at that
temperature. The mixture was stirred on a magnetic
stirrer at –10 to 0°C for 5 h and at 20°C for 24 h. The
solvent was removed under reduced pressure, the
residue was dissolved in 20 mL of chloroform, and the
solution was washed with a saturated aqueous solution
of NaHCO3 and dried over CaCl2. The solvent was
removed under reduced pressure, and the solid residue
was subjected to alumina chromatography.
1
analyzed by TLC and H NMR. The major product
(3a or 3b) was isolated by alumina column chroma-
tography.
6-syn-(Benzenesulfonyl)-7-exo-(phenyldiazenyl)-
bicyclo[3.1.1]heptane (3a). Yield 240 mg (26.2%),
yellow crystals, mp 130–131°C (decomp., from
acetone–petroleum ether). IR spectrum, ν, cm–1:
2955 w, 1477 w (N=N), 1447 m, 1308 s (SO2, asym.),
1285 s, 1146 v.s (SO2, sym.), 1088 m, 721 v.s, 687 s,
1
617 v.s. H NMR spectrum, δ, ppm: 1.87–1.98 m
(1H, endo-3-H), 2.05–2.21 m (3H, exo-3-H, endo-2-H,
endo-4-H), 2.82–2.89 m (2H, exo-2-H, exo-4-H),
3.04 br.s (2H, 1-H, 5-H), 4.20 s (1H, endo-6-H), 4.60 t
(1H, anti-7-H, J = 5.8 Hz), 7.42–7.44 m (3H, Harom),
7.56–7.65 m (5H, Harom), 7.94–7.96 m (2H, Harom).
13C NMR spectrum, δC, ppm: 14.6 (C3), 23.3 (C2, C4),
6-syn-(4-Methylbenzenesulfonyl)-7-exo-phenyl-
bicyclo[3.1.1]heptane (4b). Yield 195 mg (6.1%),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 4 2020

KOSTRYUKOV, MASTEROVA
580
colorless crystals, mp 134–135°C (from CHCl3–
petroleum ether). IR spectrum, ν, cm–1: 2956 m,
1599 w, 1312 s (SO2, asym.), 1290 s, 1144 s (SO2,
sym.), 1084 m, 827 m, 770 w, 680 v.s, 601 m. 1H NMR
spectrum, δ, ppm: 1.88–1.97 m (1H, endo-3-H), 2.04–
2.26 m (1H, exo-3-H), 2.43 s (3H, CH3C6H4), 2.66–
2.79 m (2H, endo-2-H, endo-4-H), 2.81–2.88 m (2H,
exo-2-H, exo-4-H), 3.02 br.d (2H, 1-H, 5-H), 3.19 s
(1H, endo-6-H), 3.61 t (1H, anti-7-H, J = 5.9 Hz),
7.33 d (2H, Harom, J = 7.9 Hz), 7.40–7.44 m (3H,
residue was dissolved in 20 mL of THF, and a solution
of 1 g of sodium carbonate in 10 mL of water was
added. The mixture was refluxed with stirring on
a magnetic stirrer for 3 h. The solvent was removed
under reduced pressure, the residue was dissolved in
15 mL of chloroform, and the solution was washed
with 5 mL of 5% aqueous sodium hydroxide to remove
benzenethiol and dried over CaCl2. The solvent was
removed under reduced pressure, and the residue was
recrystallized from acetone–petroleum ether. Yield
0.82 g (62%), mp 136–137°C. IR spectrum, ν, cm–1:
2955 w, 1782 v.s (C=O), 1597 w, 1319 m (SO2, asym.),
1288 s, 1146 v.s (SO2, sym.), 1088 m, 694 m, 671 s,
H
arom), 7.60–7.64 m (2H, Harom), 7.79 d (2H, Harom, J =
8.2 Hz). 13C NMR spectrum, δC, ppm: 14.6 (C3), 21.6
(CH3C6H4), 24.6 (C2, C4), 43.0 (C1, C5), 44.8 (C6),
60.0 (C7), 122.3 (2C, Carom), 126.9 (2C, Carom), 127.5
(2C, Carom), 130.0 (2C, Carom), 130.8 (Carom), 137.6
(Carom), 139.3 (Carom), 144.7 (Carom). Mass spectrum,
m/z (Irel, %): 326 (4) [M]+, 171 (45), 156 (38), 145 (20),
129 (22), 91 (100). Found, %: C 73.55; H 6.76.
C20H22O2S. Calculated, %: C 73.58; H 6.79.
1
586 m. H NMR spectrum, δ, ppm: 1.68–1.77 m (1H,
endo-3-H), 2.91–1.98 m (1H, exo-3-H), 2.22–2.27 m
(2H, endo-2-H, endo-4-H), 2.45 s (3H, CH3C6H4SO2),
3.25–3.30 m (4H, exo-2-H, exo-4-H, 1-H, 5-H), 3.45 t
(1H, anti-7-H, J = 6.0 Hz), 7.37 d (2H, Harom, J =
8.0 Hz), 7.80 d (2H, Harom, J = 8.1 Hz). 13C NMR
spectrum, δC, ppm: 16.7 (C3), 21.6 (CH3C6H4), 27.5
(C2, C4), 53.1 (C1, C5), 60.2 (C7), 127.3 (2C, Carom),
130.2 (2C, Carom), 138.0 (Carom), 145.0 (Carom), 206.1
(C6=O). Mass spectrum, m/z (Irel, %): 264 (3) [M]+,
249 (10), 156 (41), 109 (50), 91 (100). Found, %:
C 63.59; H 6.13. C14H16O3S. Calculated, %: C 63.61;
H 6.10.
6-syn-(4-Methylbenzenesulfonyl)-7-endo-phenyl-
bicyclo[3.1.1]heptane (9b). Yield 1.66 g (50.8%),
colorless crystals, mp 150–151°C (from CHCl3–
petroleum ether). IR spectrum, ν, cm–1: 2957 m,
1600 w, 1315 s (SO2, asym.), 1291 s, 1147 s (SO2,
sym.), 1085 m, 830 m, 775 w, 685 v.s, 608 m. 1H NMR
spectrum, δ, ppm: 0.63–0.86 m (1H, endo-3-H), 1.44–
1.59 m (1H, exo-3-H), 2.44 s (3H, CH3C6H4), 1.78–
1.95 m (2H, endo-2-H, endo-4-H), 2.42–2.65 m (2H,
exo-2-H, exo-4-H), 3.15 br.d (2H, 1-H, 5-H), 2.91 t
(1H, exo-6-H, J = 5.9 Hz), 3.38 t (1H, anti-7-H, J =
5.9 Hz), 7.28 d (2H, Harom, J = 7.9 Hz), 7.36–7.42 m
(3H, Harom), 7.57–7.61 m (2H, Harom), 7.71 d (2H,
Phenylhydrazones 6a and 6b (general procedure).
A solution of 3 mmol of ketone 7a or 7b in 7 mL of
dioxane was added in small portions under continuous
stirring to a solution of 477 mg (3.3 mmol) of phenyl-
hydrazine hydrochloride and 250 mg (3 mmol) of
anhydrous sodium acetate in 7 mL of water. The
mixture was stirred at room temperature for 2 h, and
the precipitate was filtered off, dried in air, and recrys-
tallized from ethanol.
H
arom, J = 8.2 Hz). 13C NMR spectrum, δC, ppm: 13.6
(C3), 21.0 (CH3C6H4), 20.4 (C2, C4), 40.4 (C6), 41.8
(C1, C5), 60.7 (C7), 121.9 (2C, Carom), 126.4 (2C,
Carom), 127.0 (2C, Carom), 129.8 (2C, Carom), 130.1
(Carom), 136.2 (Carom), 138.9 (Carom), 142.0 (Carom).
Mass spectrum, m/z (Irel, %): 326 (4) [M]+, 171 (40),
156 (35), 145 (25), 129 (30), 91 (100). Found, %:
C 73.55; H 6.76. C20H22O2S. Calculated, %: C 73.58;
H 6.79.
7-endo-(Benzenesulfonyl)bicyclo[3.1.1]heptan-2-
one phenylhydrazone (6a). Yield 0.84 g (82.3%),
mp 174–175°C. IR spectrum, ν, cm–1: 2961 w, 1602 s,
1505 w, 1449 m, 1312 s (SO2, asym.), 1291 s, 1150 v.s
(SO2, sym.), 1091 m, 720 v.s, 680 s, 622 v.s. 1H NMR
spectrum, δ, ppm: 1.32–1.36 m (1H, endo-3-H), 1.44–
1.49 m (1H, exo-3-H), 1.52–1.74 m (4H, endo-2-H,
endo-4-H), 2.02–2.11 m (2H, exo-2-H, exo-4-H),
3.44 br.d (2H, 1-H, 5-H), 3.68 t (1H, exo-7-H, J =
5.8 Hz), 7.42–7.44 m (3H, Harom), 7.06–7.31 m (5H,
Independent synthesis of 7-endo-(4-methylben-
zenesulfonyl)bicyclo[3.1.1]heptan-6-one (7b). A so-
lution of 1.01 g (5 mmol) of 1-(phenylsulfanyl)tri-
cyclo[4.1.0.02,7]heptane (10) in 4 mL of methylene
chloride was mixed with a solution of 1.17 g (5 mmol)
of 4-methylbenzenesulfonyl bromide in 4 mL of
methylene chloride, and the mixture was irradiated in
a hermetically closed quartz test tube for 10 h. The
solvent was removed under reduced pressure, the
H
arom), 7.94–7.96 m (2H, Harom), 9.87 s (1H, NH).
13C NMR spectrum, δC, ppm: 13.9 (C3), 24.3 (C2, C4),
42.2 (C1, C5), 58.1 (C7), 118.2 (2C, Carom), 125.2 (2C,
Carom), 128.1 (2C, Carom), 129.2 (2C, Carom), 129.8
(Carom), 138.4 (Carom), 144.7 (Carom), 151.7 (Carom),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 4 2020

REACTION OF TRICYCLO[4.1.0.02,7]HEPTANE
581
153.6 (C6). Mass spectrum, m/z (Irel, %): 340 (4) [M]+,
REFERENCES
235 (15), 222 (34), 199 (58), 157 (39), 142 (100), 107
(50). Found, %: C 67.09; H 5.88; N 8.29. C19H20N2O2S.
Calculated, %: C 67.03; H 5.92; N 8.23.
1. Kamigata, N., Kondoh, T., Kameyama, M., Satoh, T.,
and Kobayashi, M., Chem. Lett., 1987, vol. 16, p. 347.
https://doi.org/10.1246/cl.1987.347
7-endo-(4-Methylbenzenesulfonyl)bicyclo[3.1.1]-
heptan-2-one phenylhydrazone (6b). Yield 0.90 g
(85%), mp 189–190°C. IR spectrum, ν, cm–1: 2959 m,
1599 s, 1504 w, 1450 m, 1316 s (SO2, asym.), 1290 s,
1156 v.s (SO2, sym.), 1094 m, 718 v.s, 675 s, 620 v.s.
1H NMR spectrum, δ, ppm: 1.30–1.34 m (1H, endo-
3-H), 1.41–1.45 m (1H, exo-3-H), 1.53–1.70 m (2H,
endo-2-H, endo-4-H), 2.06–2.14 m (2H, exo-2-H, exo-
4-H), 2.45 s (3H, CH3C6H4), 3.14 br.d (2H, 1-H, 5-H),
3.48 t (1H, exo-7-H, J = 5.8 Hz), 7.28 d (2H, Harom, J =
7.9 Hz), 7.28–7.39 m (3H, Harom), 7.47–7.51 m (2H,
2. Kamigata, N., Satoh, A., and Yoshida, M., Phosphorus,
Sulfur Silicon Relat. Elem., 1989, vol. 46, p. 121.
https://doi.org/10.1080/10426508909412057
3. Kamigata, N., Satoh, A., Kondoh, T., and Kame-
yama, M., Bull. Chem. Soc. Jpn., 1988, vol. 61, p. 3575.
https://doi.org/10.1246/bcsj.61.3575
4. Rosenthal, A.J. and Overberger, C.G., J. Am. Chem.
Soc., 1960, vol. 82, p. 108.
https://doi.org/10.1021/ja01486a024
5. Cholvad, V., Szaboova, K., and Staško, A., Magn. Reson.
Chem., 1991, vol. 29, p. 402.
https://doi.org/10.1002/mrc.1260290421
H
arom), 7.71 d (2H, Harom, J = 8.2 Hz), 9.86 s (1H, NH).
6. Dossena, A., Sampaolesi, S., Palmieri, A., Protti, S., and
Fagnoni, M., J. Org. Chem., 2017, vol. 82, p. 10687.
https://doi.org/10.1021/acs.joc.7b01532
7. Onuigbo, L., Raviola, C., Di Fonzo, A., Protti, S., and
Fafnoni, M., Eur. J. Org. Chem., 2018, vol. 2018,
p. 5297.
https://doi.org/10.1002/ejoc.201800883
8. Vasin, V.A., Kostryukov, S.G., and Razin, V.V., Russ. J.
Org. Chem., 1996, vol. 32, p. 49.
9. Vasin, V.A., Bolusheva, I.Yu., Chernyaeva, L.A.,
Surmina, L.S., and Zefirov, N.S., Zh. Org. Khim., 1990,
vol. 26, p. 1509.
10. Vasin, V.A., Razin, V.V., and Kostryukov, S.G., Russ. J.
Org. Chem., 1996, vol. 32, p. 1657.
13C NMR spectrum, δC, ppm: 14.9 (C3), 21.3
(CH3C6H4), 25.3 (C2, C4), 50.2 (C1, C5), 59.6 (C7),
118.2 (2C, Carom), 124.2 (2C, Carom), 126.7 (2C, Carom),
129.7 (2C, Carom), 130.1 (Carom), 136.4 (Carom), 138.7
(Carom), 142.7 (Carom), 152.9 (C6). Mass spectrum, m/z
(Irel, %): 354 (4) [M]+, 339 (18), 199 (45), 171 (30),
156 (100), 107 (43). Found, %: C 67.75; H 6.28;
N 7.87. C20H22N2O2S. Calculated, %: C 67.77; H 6.26;
N 7.90.
Isomerization of bicyclo[3.1.1]heptanes 3a and
3b to phenylhydrazones 6a and 6b (general proce-
dure). A solution of 0.1 mmol of compound 3a or 3b in
2 mL of benzene was heated in a sealed ampule at 60–
70°C for 10 h. The ampule was cooled and opened, the
solvent was removed under reduced pressure, and the
residue was analyzed by 1H and 13C NMR.
11. Vasin, V.A., Razin, V.V., Kostryukov, S.G., and
Zefirov, N.S., Zh. Org. Khim., 1994, vol. 30, p. 680.
12. Vasin, V.A., Masterova, Yu.Yu., Razin, V.V., and
Somov, N.V., Can. J. Chem., 2013, vol. 91, p. 465.
https://doi.org/10.1139/cjc-2012-0159
Hydrolysis of compounds 3a and 3b (general
procedure). A flat-bottom flask equipped with a mag-
netic stirrer was charged with a solution of 0.3 mmol of
compound 3a or 3b in a mixture of 15 mL of THF and
1 mL of water. The mixture was heated at 50–55°C for
4 h (TLC), the solvent was removed under reduced
pressure, and the residue was recrystallized from
acetone–petroleum ether. Yield: 7a, 61 mg (82%);
7b, 63 mg (80%).
13. Vasin, V.A., Korovin, D.Yu., Razin, V.V., and
Petrov, P.S., Russ. J. Org. Chem., 2019, vol. 55, p. 415.
https://doi.org/10.1134/S1070428019040018
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1970, vol. 92, p. 2090.
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Russ. J. Org. Chem., 1991, vol. 27, p. 1253
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Harnisch, J., Tetrahedron Lett., 1977, vol. 18, p. 2135.
https://doi.org/10.1016/S0040-4039(01)83700-X
17. Kojima, M., Minato, H., and Kobayashi, M., Bull. Chem.
Soc. Jpn., 1972, vol. 45, p. 2032.
CONFLICT OF INTEREST
The authors declare the absence of conflict of interest.
https://doi.org/10.1246/bcsj.45.2032
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 4 2020