Reaction of substituted 1,2,8,9-tetraazadispiro[4.1.4.3]tetradeca-1,8-dien- 6-ones and 1,2,8,9-tetraazadispiro[4.1.4.2]trideca-1,8-dien-6-ones with chlorine

Article abstract of DOI:10.1007/s10593-008-0060-2

Reaction of 4,11-diaryl-1,2,8,9-tetraazadispiro[4.1.4.3]tetradeca-1,8-dien- 6-ones and-dispiro[4.1.4.2]trideca-1,8-dien-6-ones with chlorine gives substituted dispirocyclic compounds containing a 3-chloro-1-pyrazoline fragment which loses nitrogen on heating to give spirocyclic chlorocyclopropanes.

Full text of DOI:10.1007/s10593-008-0060-2

Chemistry of Heterocyclic Compounds, Vol. 44, No. 4, 2008
REACTION OF SUBSTITUTED 1,2,8,9-TETRA-
AZADISPIRO[4.1.4.3]TETRADECA-1,8-DIEN-6-ONES
AND 1,2,8,9-TETRAAZADISPIRO[4.1.4.2]TRIDECA-
1,8-DIEN-6-ONES WITH CHLORINE
A. P. Molchanov1, A. A. Eremeeva1, J. Kopf2, and R. R. Kostikov1
Reaction of 4,11-diaryl-1,2,8,9-tetraazadispiro[4.1.4.3]tetradeca-1,8-dien-6-ones and -dispiro-
[4.1.4.2]trideca-1,8-dien-6-ones with chlorine gives substituted dispirocyclic compounds containing a
3-chloro-1-pyrazoline fragment which loses nitrogen on heating to give spirocyclic chlorocyclo-
propanes.
Keywords: diazomethane, pyrazolines, cyclopropane.
It has previously been shown that the reactions of bi- and spirocyclic 2-pyrazolines with halogenating
agents give substituted 3-halo-1-pyrazolines which lose nitrogen on heating to give substituted 1-halo-
cyclopropane-1-carboxylates [1-7]. The halogenation of spirocyclic 1-pyrazolines, obtained from diazomethane
and itaconic acid imides gives spirocyclic mono- and dihalocyclopropanes [8] while the chlorination of
4'-arylspiro[1,2,3,4-tetrahydronaphthalene-2,3'-(1'-pyrazolin)]-1-ones gives the corresponding 3-chloro-1-pyrazo-
lines which lose nitrogen on heating to form spirocyclic chlorocyclopropanes [9].
In this work we have studied the reaction of the 4,11-diaryl-1,2,8,9-tetraazadispiro[4.1.4.3]tetradeca-
1,8-dien-6-ones 1a-c and the 4,11-diaryl-1,2,8,9-tetraazadispiro[4.1.4.2]trideca-1,8-dien-6-ones 2a-c with
chlorine and subsequent thermolysis of obtained 3-chloro-1-pyrazolines. The pyrazolines 1a-c and 2a-c were
prepared by the reaction of diazomethane with 2,6-bis[(E)-arylmethylidene]-1-cyclohexanones 3a-c and
1
2,5-bis[(E)-arylmethylidene]-1-cyclopentanones 4a-c respectively. Using H NMR spectroscopy it was shown
that the reaction mixture of dienes 3a-c and 4a-c with diazomethane contains two diastereomer compounds in
the ratios 4:1 and 5:1 respectively. The main isomers 1a-c and 2a-c were separated by recrystallization.
H
O
O
O
N
N
N N
N
N
H
H
H
Ar
N
Ar
CH2N2
Ar
N
+
( )
( )
( )
Ar
Ar
Ar
n
n
n
1'a-c, 2'a-c
3a-c, 4a-c
1a-c, 2a-c
a Ar = Ph, b Ar = 4-ClC6H4, c Ar = 4-MeOC6H4, 1, 3 n = 1; 2, 4 n = 0
__________________________________________________________________________________________
1St. Petersburg State University, St. Petersburg 198504, Russia; e-mail: s.lab@pobox.spbu.ru. 2Inorganic
Chemistry Institute, Hamburg, D-20146, Germany; e-mail: kopf@xray.chemie.uni-hamburg.de. Translated from
Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 558-566, April, 2008. Original article submitted October
12, 2007.
0009-3122/08/4404-0435©2008 Springer Science+Business Media, Inc.
435

The structure of the pyrazolines 1a-c and 2a-c was shown from spectroscopic data. Hence the 1H NMR
spectrum of the pyrazoline 1a shows: a signal for the pyrazoline ring methine group proton as a double doublet
at 3.90 ppm (J = 9 and J = 3 Hz), signals for the CH2 group protons at 4.69 ppm (dd, J = 18 and J = 9 Hz) and
5.05 ppm (dd, J = 18 and J = 3 Hz), and also signals for the aromatic and cyclohexane rings protons. It has
previously been shown that, in the product of addition of diazomethane to the structurally similar 2-benzylidene-
1-tetralone, the aryl group occurs in a trans position relative to the carbonyl group [9].
The reaction of the spiropyrazolines 1a-c and 2a-c with excess chlorine in chloroform at -10ºC gives
63-84% yields of the substituted 3,10-dichloro-1,2,8,9-tetraazadispiro[4.1.4.3]tetradeca-1,8-dien-6-ones 5a-c
and 3,10-dichloro-1,2,8,9-tetraazadispiro[4.1.4.2]trideca-1,8-dien-6-ones 6a-c.
H
Cl
O
N
N
H
Cl
H
Ar
N
N
Cl2
1a–c, 2a–c
H
( )
Ar
n
5a–c, 6a–c
5, 6 a Ar = Ph, b Ar = 4-ClC6H4, c Ar = 3-Cl-4-MeOC6H3; 5 n = 1, 6 n = 0
The composition and structure of the compounds were established by their spectroscopic and elemental
1
analytical data. The H NMR spectra of the reaction mixture showed signals for only one of the possible
diastereomers: signals for the cyclohexane ring protons at 1.68-2.27 ppm, doublet signals for the H-4 and H-11
group protons at 3.73-4.23 ppm, and signals for the H-3 and H-10 protons at 6.28-6.37 ppm (d, J = 5 Hz). The
13C NMR spectra show signals for the quaternary carbon atoms of the pyrazoline rings at 104.0-105.0, the C-3
and C-10 atom signals at 96.5-98.4 ppm, and the carbonyl carbon atom signal at 197-204 ppm. It should be
noted that chlorination of pyrazolines 1c and 2c with donor substituents in the ring also chlorinates the aromatic
ring. The chloro-substituted pyrazolines are unstable at room temperature and slowly decompose hence
satisfactory elemental analytical data could not be obtained for all of the compounds.
H
Cl
Cl
O
O
H
N
N
Cl2, 0°C
Cl
Cl
H
60°C
Cl
Cl
Cl
Cl
H
Ar
N
2b
N
Ar
Ar
Ar
7
Ar = 4-ClC6H4
The chlorination of the pyrazoline 2b at 0ºC also gives a tetrachloro-substituted pyrazoline which loses
nitrogen at 60ºC to form 1,1,6,6-tetrachloro-2,7-bis(4-chlorophenyl)dispiro[2.1.2.2]nonan-4-one (7).
Heating the chloropyrazolines 5a,b and 6a,b in ethanol for 0.5 h gives a good yield of the products of
extrusion of nitrogen from only one of the pyrazoline rings, i.e. compounds 8a,b and 9a,b. According to
1H NMR spectroscopy the reaction mixtures contains only a single stereoisomer.
O
N
N
H
Cl
Cl
H
EtOH, 60°C
Ar
5a,b, 6a,b
H
( )
H
Ar
8a,b, 9a,b
8, 9 a Ar = Ph, b Ar = 4-ClC6H4; 8 n = 1, 9 n = 0
n
436

The composition and structure of the compounds were determined from spectroscopic and elemental
analytical data. The IR spectra of the compounds show absorption stretching bands for the carbonyl groups at
1
1690-1710 cm-1. The H NMR spectra show signals for the pyrazoline ring protons at 3.73-4.00 and 6.21-6.33
ppm and doublet signals for the protons of the cyclopropane ring at 2.95-3.15 and 3.50-3.75 ppm (J = 6 Hz).
1
The main interactions between the protons were obtained from the H−1H NOESY spectra of compound 8b
(Figure 1) in which cross peaks are present corresponding to interaction of both cyclopropane ring protons with
the ortho protons of the aromatic ring and also cross peaks relating to interaction of both pyrazoline ring protons
with the ortho protons of the second aromatic ring. Hence we deduce that the chlorine atom is trans related to
the aryl substituent in the pyrazoline ring.
O
O
N
N
N
N
H
Cl
H
Cl
Cl
H
Cl
H
Ar
H
Ar
H
H
H
H
Ar
H
Ar
H1
H4
H3
H2
H
H
a
b
Fig. 1. Main proton interaction obtained from the 1H−1H NOESY spectra
of compound 8b (a) and 9a (b).
From consideration of the intensity of the cross peaks in the 1H−1H NOESY spectra of compound 9a we
can deduce that the H-1 and H-2 protons can be assigned to one carbon and protons H-3 and H-4 to the other
carbon atom in the cyclopentane ring while the H-1 proton occurs close to proton H-4 and proton H-2 near to
proton H-3. The structure shown in the Figure is chosen because the hydrogen atom shifted to lower field is
situated close to the aryl substituent (in this case H-1 and H-3).
Further heating of compounds 8a,b and 9a,b gave the substituted 1,6-dichlorodispiro[2.1.2.3]decan-
4-ones 10a,b and 1,6-dichlorodispiro[2.1.2.2]nonan-4-ones 11a,b in 86-91% yield. The spectra of the reaction
mixtures point to the presence of signals for only one isomer.
Fig. 2. X-ray structure of compound 10b.
The composition and structure of the compounds are based on their spectroscopic and elemental
1
analytical data. The H NMR spectra show signals for the protons of the tricyclic ring as a CHCl group at
3.26-3.31 and CHAr at 3.70-3.75 ppm and also for the aromatic protons and the protons of the cyclohexane or
cyclopentane ring. The 13C NMR spectra of compounds 10a,b show signals for the carbon atom of the
cyclohexane ring at 20.2-20.3 and 26.7-26.8 ppm, the CH groups of the cyclopropane ring at 37.5-38.2 and
44.3-44.4 ppm, the quaternary carbon atoms (41 ppm), and also signals for the aromatic ring atoms and carbonyl
437

group (199 ppm). The carbon atoms of the cyclopropane ring are shifted to higher field when compared with the
signals of the pyrazoline ring carbon atoms. The IR spectrum of compound 10b shows carbonyl group stretching
absorption at 1675 cm-1.
The structure of compound 10b was proved by X-ray structural analysis (Fig. 2).
Hence we can deduce that the reaction of diazomethane with 2,6-bis(arylmethylidene)cyclohexanones
and 2,5-bis(arylmethylidene)cyclopentanones occurs regioselectively with the principal formation of the
stereoisomer arising from syn,anti attack of two diazomethane molecules. Chlorination of the pyrazolines
formed and subsequent extrusion of nitrogen occurs regio- and stereospecifically to give chlorocyclopropane-
spirocycloalkane-spirochlorocyclopropane systems with (RS, RS)-configured spiroatoms.
EXPERIMENTAL
1
IR spectra were obtained on a Specord 75 IR spectrophotometer using KBr. H and 13C NMR spectra
were recorded on a Bruker DPX-300 (300 and 75 MHz) instrument for compounds solutions in DMSO-d6 or
CDCl3 (compounds 1, 2, 5-7, 9-11). Chemical shifts are quoted relative to the residual signals of
1
deuterochloroform or DMSO-d6 (7.26 and 2.50 ppm respectively for H NMR). Checking of the purity of the
products and analysis of the reaction mixtures was carried out TLC using Silufol UV-254 plates.
Elemental analysis of compounds 1a-c, 2a-c, 5a-c, 6b, 7 and 9b did not prove possible because they are
thermally unstable.
Preparation of Pyrazolines 1a-c, 2a-c (General Method). An ether solution of diazomethane prepared
from N-nitrosomethylurea (10 g, 0.1 mol) was added to a cold solution of the corresponding diene 3a-c, 4a-c
(4 mmol) in chloroform (15 ml). The reaction mixture was left overnight, solvent was evaporated, and the
residue was recrystallized from ethanol.
4,11-Diphenyl-1,2,8,9-tetraazadispiro[4.1.4.3]tetradeca-1,8-dien-6-one (1a). Yield 80%; mp
114-115ºC (decomp.). 1H NMR spectrum, δ, ppm (J, Hz): 1.77 (2H, m, CH2); 1.88 (2H, m, CH2); 2.19 (2H, m,
CH2); 3.90 (2H, dd, J = 8.7, J = 2.9, H-3(10)); 4.69 (2H, dd, J = 18.2, J = 8.7, H-10(3)); 5.05 (2H, dd, J = 18.2,
J = 2.9, H-4(11)); 7.01 (4H, d, J = 6.5, ArH); 7.20-7.38 (6H, d, ArH). 13C NMR spectrum, δ, ppm: 18.9 (CH2);
31.8 (CH2); 43.4 (CH); 84.5 (CH2); 104.2 (C), 127.9 (CH); 129.0 (CH); 129.1 (CH); 138.3 (C); 198.7 (CO).
4,11-Bis(4-chlorophenyl)-1,2,8,9-tetraazadispiro[4.1.4.3]tetradeca-1,8-dien-6-one (1b). Yield 82%;
mp 137-138ºC (decomp.). 1H NMR spectrum, δ, ppm (J, Hz): 1.77 (2H, m, CH2); 1.88 (2H, m, CH2); 2.20 (2H,
m, CH2); 3.87 (2H, dd, J = 8.3, J = 3.0, H-3(10)); 4.68 (2H, dd, J = 18.1, J = 8.4, H-10(3)); 4.98 (2H, dd,
J = 18.1, J = 3.0, H-4(11)); 6.94 (4H, d, J = 8.2, ArH); 7.29 (4H, d, J = 8.2, ArH). 13C NMR spectrum, δ, ppm:
18.9 (CH2); 31.9 (CH2); 42.7(CH); 84.3 (CH2); 104.1 (C); 129.3 (CH); 130.3 (CH); 133.9 (C); 136.6 (C); 198.3
(CO).
4,11-Bis(4-methoxyphenyl)-1,2,8,9-tetraazadispiro[4.1.4.3]tetradeca-1,8-dien-6-one (1c). Yield
79%; mp 143-145ºC (decomp). 1H NMR spectrum, δ, ppm (J, Hz): 1.76 (2H, m, CH2); 1.88 (2H, m, CH2); 2.19
(2H, m, CH2); 3.80 (6H, s, OCH3); 3.84 (2H, dd, J = 8.4, J = 3.0, H-3(10)); 4.65 (2H, dd, J = 18.0, J = 8.4,
H-10(3)); 4.98 (2H, dd, J = 18.0, J = 3.0, H-4(11)); 6.82 (4H, d, J = 7.5, ArH); 6.92 (4H, d, J = 7.5, ArH).
13C NMR spectrum, δ, ppm: 18.7 (CH2); 31.5 (CH2); 42.4 (CH); 55.4 (CH3); 84.2 (CH2); 103.9 (C); 114.1
(CH); 129.7 (CH); 129.8 (C); 158.9 (C); 198.5 (CO).
4,11-Diphenyl-1,2,8,9-tetraazadispiro[4.1.4.2]trideca-1,8-dien-6-one (2a). Yield 85; mp 117-119ºC
(decomp). 1H NMR spectrum, δ, ppm (J, Hz): 2.19 (4H, m, CH2CH2); 3.49 (2H, dd, J = 8.4, J = 3.4, H-3(10));
4.99 (2H, dd, J = 18.1, J = 8.4, H-10(3)); 5.13 (2H, dd, J = 18.1, J = 3.4, H-4(11)); 6.91 (4H, d, J = 7.5, ArH);
7.22-7.31 (6H, m, ArH). 13C NMR spectrum, δ, ppm: 28.4 (CH2); 44.0 (CH); 85.8 (CH2); 105.5 (C); 127.6
(CH); 127.8 (CH); 128.9 (CH); 138.8 (C); 206.3 (CO).
438

4,11-Bis(4-chlorophenyl)-1,2,8,9-tetraazadispiro[4.1.4.2]trideca-1,8-dien-6-one (2b). Yield 81%; mp
126-128ºC (decomp.). 1H NMR spectrum, δ, ppm (J, Hz): 2.19 (4H, m, CH2CH2); 3.46 (2H, dd, J = 8.2, J = 3.4,
H-3(10)); 4.95 (2H, dd, J = 18.1, J = 8.4, H-10(3)); 5.06 (2H, dd, J = 18.1, J = 3.4, H-4(11)); 6.83 (4H, d,
J = 8.5, ArH); 7.24 (4H, d, J = 8.5, ArH). 13C NMR spectrum, δ, ppm: 28.9 (CH2); 43.8 (CH); 86.3 (CH2);
105.9 (C); 129.6 (CH); 130.0 (CH); 134.0 (C); 137.8 (C); 206.2 (CO).
4,11-Bis(4-methoxyphenyl)-1,2,8,9-tetraazadispiro[4.1.4.2]trideca-1,8-dien-6-one (2c). Yield 76%;
1
mp 129-132ºC (decomp.). H NMR spectrum, δ, ppm (J, Hz): 2.19 (4H, m, CH2CH2); 3.45 (2H, dd, J = 8.2,
J = 3.5, H-3(10)); 4.99 (2H, dd, J = 18.0, J = 8.2, H-10(3)); 5.06 (2H, dd, J = 18.0, J = 3.5, H-4(11)); 6.75-6.87
(8H, m, ArH).
Preparation of the Chloropyrazolines 5a-c, 6a-c (General Method). A solution of the pyrazoline 1a-c
or 2a-c (5 mmol) in chloroform (20 ml) was cooled to -10ºC and a stream of chlorine was passed through and
monitored by TLC to the disappearance of the starting pyrazoline. The mixture was warmed to room
temperature and separated from an admixture on a column eluting with a 6:1 mixture of hexane and ethyl
acetate. Solvent was evaporated off and the precipitate was recrystallized from alcohol.
3,10-Dichloro-4,11-diphenyl-1,2,8,9-tetraazadispiro[4.1.4.3]tetradeca-1,8-dien-6-one (5a). Yield
84%; mp 115-117ºC (decomp.). IR spectrum, ν, cm-1: 835 s, 1090 s, 1190, 1320, 1360, 1505 s, 1685, 1700,
2950. 1H NMR spectrum, δ, ppm (J, Hz): 1.68 (2H, m, CH2); 1.82 (2H, m, CH2); 2.15 (2H, m, CH2); 4.23 (2H,
d, J = 5.0, H-4(11)); 6.37 (2H, d, J = 5.0, CHCl); 7.12 (4H, d, J = 7.7, ArH); 7.30-7.45 (6H, m, ArH). 13C NMR
spectrum, δ, ppm: 18.3 (CH2); 33.5 (2CH2); 51.3 (CH), 96.5 (CH); 104.3 (C); 128.7 (CH); 129.1 (CH); 129.4
(CH); 134.5 (C); 197.8 (CO).
3,10-Dichloro-4,11-bis(4-chlorophenyl)-1,2,8,9-tetraazadispiro[4.1.4.3]tetradeca-1,8-dien-6-one
(5b). Yield 84%; mp 123-125ºC (decomp.). IR spectrum, ν, cm-1: 825 s, 1010, 1090 s, 1490 s, 1710 s, 2960.
1H NMR spectrum, δ, ppm (J, Hz): 1.70 (2H, m, CH2); 1.82 (2H, m, CH2); 2.15 (2H, m, CH2); 4.18 (2H, d,
J = 5.1, H-4(11)); 6.31 (2H, d, J = 5.1, CHCl); 7.07 (4H, d, J = 7.8, ArH); 7.35 (4H, d, J = 7.8, ArH). 13C NMR
spectrum, δ, ppm: 17.9 (CH2); 33.0 (2CH2); 50.4 (CH); 95.9 (CH); 103.7 (C); 129.3 (CH); 130.0 (CH); 132.4
(C); 134.4 (C); 197.1 (CO).
3,10-Dichloro-4,11-bis(3-chloro-4-methoxyphenyl)-1,2,8,9-tetraazadispiro[4.1.4.3]tetradeca-1,8-
dien-6-one (5c). Yield 75%; mp 133-135ºC (decomp.). 1H NMR spectrum, δ, ppm (J, Hz): 1.72 (2H, m, CH2);
1.85 (2H, m, CH2); 2.19 (2H, m, CH2); 3.91 (6H, s, OCH3); 4.14 (2H, d, J = 5.1, H-4(11)); 6.28 (2H, d, J = 5.1,
13
CHCl); 6.91 (2H, d, J = 8.7, ArH); 7.00 (2H, dd, J = 8.7, J = 2.2, ArH); 7.12 (2H, d, J = 2.2, ArH). C NMR
spectrum, δ, ppm: 18.0 (CH2); 33.1 (2CH2); 50.1 (CH); 56.2 (CH3); 95.9 (CH); 103.6 (C); 112.4 (CH); 123.1
(C); 126.7 (C); 128.4 (CH); 130.0 (CH); 155.9 (C); 197.2 (CO).
3,10-Dichloro-4,11-diphenyl-1,2,8,9-tetraazadispiro[4.1.4.2]trideca-1,8-dien-6-one (6a). Yield 78%;
mp 129-131ºC (decomp.). 1H NMR spectrum, δ, ppm (J, Hz): 1.95 (2H, m, CH2); 2.18 (2H, m, CH2); 3.76 (2H,
d, J = 6.2, H-4(11)); 6.38 (2H, d, J = 6.2, CHCl); 7.00 (4H, dd, J = 7.6, J = 1.7, ArH); 7.29-7.34 (6H, m, ArH).
13C NMR spectrum, δ, ppm: 28.9 (CH2), 52.7 (CH), 98.0 (CH), 104.5 (C), 128.1 (CH), 128.4 (CH), 129.3 (CH),
134.4 (C), 203.2 (CO). Found, %: C 61.04; H 4.36; N 13.45. C21H18Cl2N4O. Calculated, %: C 61.04; H 4.39; N
13.56.
3,10-Dichloro-4,11-bis(4-chlorophenyl)-1,2,8,9-tetraazadispiro[4.1.4.2]trideca-1,8-dien-6-one (6b).
1
Yield 72%; mp 135-137ºC (decomp.). H NMR spectrum, δ, ppm (J, Hz): 1.95 (2H, m, CH2); 2.19 (2H, m,
CH2); 3.73 (2H, d, J = 6.2, H-4(11)); 6.32 (2H, d, J = 6.2, CHCl); 6.95 (4H, d, J = 8.5, ArH); 7.37 (4H, d,
J = 8.5, ArH). 13C NMR spectrum, δ, ppm: 28.8 (CH2), 52.1 (CH), 97.7 (CH), 104.1 (C), 129.3 (CH), 129.5
(CH), 131.0 (C), 134.5 (C), 202.8 (CO).
1,1,6,6-Tetrachloro-2,7-bis(4-chlorophenyl)dispiro[2.1.2.2]nonan-4-one (7). A stream of chlorine
was passed through a solution of the pyrazoline 2b (5 mmol) in chloroform (20 ml) at 0ºC and monitored by
TLC to the disappearance of starting material. The mixture was warmed to room temperature, chloroform was
evaporated, and the product 7 was separated on a silica gel column using a 6:1 mixture of hexane and ethyl
439

1
acetate as eluent. Yield 12%; mp 151-153ºC (alcohol). H NMR spectrum, δ, ppm (J, Hz): 2.41 (4H, s,
13
CH2CH2); 3.56 (2H, s, H-2(7)); 7.23 (4H, d, J = 8.1, ArH); 7.38 (4H, d, J = 8.1, ArH). C NMR spectrum, δ,
ppm: 26.5 (2 CH2), 41.7 (CH), 48.0 (C), 67.1 (C), 128.9 (CH), 129.9 (C), 131.0 (CH), 134.2 (C), 200.6 (CO).
Preparation of Compounds 8a,b and 9a,b (General Method). A solution of the corresponding
chloropyrazoline (4 mmol) in ethanol (60 ml) was refluxed for 30 min and monitored by TLC. The solvent was
partially distilled off, cooled, and the precipitate formed was filtered off.
2,8-Dichloro-1,9-diphenyl-6,7-diazadispiro[2.1.4.3]dodecan-4-one (8a). Yield 92%; mp 135-136ºC
1
(decomp.). IR spectrum, ν, cm-1: 930, 1085 s, 1250, 1290, 1440, 1490, 1710 s, 2965. H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 1.32 (1H, m, CH2); 1.68 (1H, m, CH2); 1.72 (1H, m, CH2); 1.78 (1H, m, CH2); 1.96
(1H, m, CH2); 2.10 (1H, m, CH2); 3.65 (2H, s, CHAr, CHCl); 4.00 (1H, d, J = 6.6, CHAr); 6.33 (1H, d, J = 6.6,
1
CHCl); 7.14 (2H, d, J = 6.0, ArH); 7.24-7.39 (8H, m, ArH). H NMR spectrum (C6D6), δ, ppm (J, Hz): 0.69
(1H, m, CH2); 0.98 (1H, m, CH2); 1.32 (1H, m, CH2); 1.46 (1H, m, CH2); 1.67 (2H, m, CH2); 3.14 (1H, d,
J = 5.8, CH); 3.73 (1H, d, J = 5.8, CH); 4.36 (1H, d, J = 7.5, CH); 6.09 (1H, d, J = 7.5, CHCl); 6.85 (2H, m,
ArH); 6.96 (2H, m, ArH); 7.11 (6H, m, ArH). 13C NMR spectrum (CDCl3), δ, ppm: 18.5 (CH2); 27.6 (CH2);
29.6 (CH2); 37.6 (CH); 40.7 (C); 44.4 (CH); 51.2 (CH); 96.8 (CH); 101.7 (C); 127.5 (CH); 128.0 (CH); 128.6
(CH); 128.7 (CH); 128.8 (CH); 128.9 (CH); 133.4 (C); 133.9 (C); 197.5 (CO). Found, %: C 65.65; H 5.19;
N 6.92. C22H20Cl2N2O. Calculated, %: C 65.84; H 5.53; N 6.98.
1,8-Dichloro-2,9-bis(4-chlorophenyl)-6,7-diazadispiro[2.1.4.3]dodecan-4-one (8b). Yield 89%; mp
1
139-140ºC (decomp.). IR spectrum, ν, cm-1: 820,1010 s, 1230, 1375, 1480 s 1690 s, 2950. H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 1.25 (1H, m, CH2); 1.39 (1H, m, CH2); 1.71 (2H, m, CH2); 2.00 (2H, m, CH2); 3.57
(1H, d, J = 5.8, CH); 3.59 (1H, d, J = 5.8, CH); 4.00 (1H, d, J = 7.3, CH); 6.25 (1H, d, J = 7.3, CHCl); 7.08 (2H,
d, J = 7.8, ArH); 7.19 (2H, d, J = 7.8, ArH); 7.30-7.40 (6H, m, ArH). 1H NMR spectrum (C6D6), δ, ppm (J, Hz):
0.59 (1H, m, CH2); 0.93 (2H, m, CH2); 1.35 (2H, m, CH2); 1.71 (1H, m, CH2); 2.95 (1H, d, J = 5.8, CH); 3.50
(1H, d, J = 5.8, CH); 4.24 (1H, d, J = 8.0, CH); 5.87 (1H, d, J = 8.0, CHCl); 6.52 (2H, d, J = 8.7, ArH); 6.65
(2H, d, J = 8.7, ArH); 7.05-7.13 (4H, m, ArH). 13C NMR spectrum (CDCl3), δ, ppm: 18.2 (CH2); 27.0 (CH2);
29.3 (CH2); 37.0 (CH); 40.3 (C); 44.1 (CH); 50.5 (CH); 96.0 (CH); 101.5 (C); 128.6 (CH); 128.9 (CH); 129.7
(CH); 129.8 (CH); 131.7 (C); 131.8 (C); 133.4 (C); 134.0 (C); 197.1 (CO). Found, %: C 56.12; H 4.09; N 5.82.
C22H18Cl4N2O. Calculated, %: C 56.19; H 4.29; N 5.96.
2,8-Dichloro-1,9-diphenyl-6,7-diazadispiro[2.1.4.2]undecan-4-one (9a). Yield 94%; mp 143-144ºC
(decomp.). 1H NMR spectrum, δ, ppm (J, Hz): 1.60 (1H, m, CH2); 1.77 (1H, m, CH2); 1.96 (1H, m, CH2); 2.33
(1H, m, CH2); 3.37 (1H, d, J = 5.6, CH); 3.75 (1H, d, J = 5.6, CH); 3.78 (1H, d, J = 7.5, CH); 6.28 (1H, d,
J = 7.5, CHCl); 7.03 (2H, d, J = 7.5, ArH); 7.19 (2H, d, J = 7.5, ArH); 7.29-7.35 (6H, m, ArH). 13C NMR
spectrum, δ, ppm: 26.3 (CH2); 29.2 (CH2); 41.4 (CH); 42.1 (C); 45.8 (CH); 52.2 (CH); 96.8 (CH); 105.2 (C);
127.8 (2CH); 128.1 (CH); 128.2 (CH); 128.8 (CH); 129.2 (CH); 133.5 (C); 134.1 (C); 203.6 (CO). Found, %:
C 65.40; H 4.81; N 7.22. C21H18Cl2N4O. Calculated, %: C 65.46; H 4.71; N 7.27.
1,8-Dichloro-2,9-di(4-chlorophenyl)-6,7-diazadispiro[2.1.4.2]undecan-4-one (9b). Yield 91%; mp
1
157-159ºC (decomp.). IR spectrum, ν, cm-1: 825, 850, 1010 s, 1090, 1220, 1490 s, 1730 s, 2950. H NMR
spectrum, δ, ppm (J, Hz): 1.61 (1H, m, CH2); 1.76 (1H, m, CH2); 1.94 (1H, m, CH2); 2.33 (1H, m, CH2); 3.33
(1H, d, J = 5.6, CH); 3.73 (2H, m, CH); 6.21 (1H, d, J = 7.5, CHCl); 6.97 (2H, d, J = 7.5, ArH); 7.14 (2H, d,
J = 7.5, ArH); 7.24-7.41 (4H, m, ArH). 13C NMR spectrum, δ, ppm: 26.4 (CH2); 29.2 (CH2); 40.6 (CH); 42.0
(C); 45.7 (CH); 51.7 (CH); 96.6 (CH); 104.9 (C); 129.1 (CH); 129.4 (CH); 129.5 (2CH); 131.9 (C); 132.3 (C);
133.8 (C); 134.3 (C); 203.2 (CO).
Preparation of Compounds 10a,b and 11a,b (General Method). A solution of compound 8a,b, 9a,b
(4 mmol) in ethanol (60 ml) was refluxed for about 40 min with monitoring by TLC, the solvent was partially
evaporated, and the precipitate was filtered off.
1
2,7-Dichloro-1,6-diphenyldispiro[2.1.2.3]decan-4-one (10a). Yield 85%; mp 213-214ºC. H NMR
spectrum, δ, ppm (J, Hz): 1.33 (2H, m, CH2); 1.71-1.76 (4H, m, CH2); 3.61 (4H, s, CHCHCl); 7.22-7.39 (10H,
440

m, ArH). 13C NMR spectrum, δ, ppm: 19.8 (CH2); 26.3 (CH2); 37.7 (CH); 41.1 (C); 43.9 (CH); 127.3 (CH);
128.4 (CH); 128.7 (CH); 134.3 (C); 199.1 (CO). Found, %: C 70.60; H 5.47. C22H20Cl2O. Calculated, %:
C 71.17; H 5.43.
1,6-Dichloro-2,7-di(4-chlorophenyl)dispiro[2.1.2.3]decan-4-one (10b). Yield 87%; mp 223-225ºC. IR
1
spectrum, ν, cm-1: 820, 1010, 1075 s, 1175, 1315, 1375, 1490 s, 1675 s, 2960. H NMR spectrum, δ, ppm (J,
Hz): 1.30 (2H, m, CH2); 1.70-1.80 (4H, m, CH2); 3.56 (4H, s, CHCHCl); 7.16 (4H, d, J = 8.4, ArH); 7.33 (4H,
d, J = 8.4, ArH). 13C NMR spectrum, δ, ppm: 19.8 (CH2); 26.3 (CH2); 37.1 (CH); 41.2 (C); 43.9 (CH); 128.8
(CH); 130.1 (CH); 132.9 (C); 133.4 (C); 199.2 (CO). Found, %: C 60.14; H 4.21. C22H18Cl4O. Calculated, %:
C 60.03; H 4.12.
1
1,6-Dichlo-2,7-diphenylrodispiro[2.1.2.2]nonan-4-one (11a). Yield 91%; mp 210-212ºC. H NMR
spectrum, δ, ppm (J, Hz): 1.76 (2H, m, CH2); 2.07 (2H, m, CH2); 3.31 (2H, d, J = 5.8, CHCl), 3.75 (2H, d,
J = 5.8, CH); 7.16 (4H, d, J = 8.2, ArH); 7.27-7.40 (6H, m, ArH). 13C NMR spectrum, δ, ppm: 26.8 (CH2); 39.1
(CH); 43.5 (C); 44.9 (CH); 127.4 (CH); 127.9 (CH); 128.7 (CH); 134.2 (C); 203.5 (CO). Found, %: C 70.09;
H 5.48. C21H18Cl2O. Calculated, %: C 70.60; H 5.08.
1,6-Dichloro-2,7-bis(4-chlorophenyl)dispiro[2.1.2.2]nonan-4-one (11b). Yield 86%; mp 219-221ºC.
1H NMR spectrum, δ, ppm (J, Hz): 1.75 (2H, m, CH2); 2.05 (2H, m, CH2); 3.26 (2H, d, J = 5.7, CHCl); 3.70
13
(2H, d, J = 5.7, CH); 7.09 (4H, d, J = 8.4, ArH); 7.33 (4H, d, J = 8.4, ArH). C NMR spectrum, δ, ppm: 26.9
(CH2); 38.3 (CH); 43.5 (C); 44.7 (CH); 129.0 (CH); 129.4 (CH); 132.7 (C); 133.5 (C); 202.9 (CO). Found, %:
C 70.09; H 5.48. C21H18Cl2O. Calculated, %: C 70.60; H 5.08.
X-ray Analysis of Compound 10b. C22H18Cl4O. M 437.14, monoclinic: space group C2/c (No. 15);
a = 19.9398(18), b = 11.4991(11), c = 9.5915(9) Å, β = 116.44(0)º, V = 1969.16(30) Å3, Z = 4, dc = 1.474 g/cm3,
Rall = 0.047, radiation source MoKα, λ = 0.71073 Å, graphite monochromator. Selected bond lengths: C(1)–
C(2) 1.762(2), O–C(4) 1.222(3), C(1)–C(2) 1.478(3), C(1)–C(3) 1.550(3), C(2)–C(3) 1.518(3), C(3)–C(4)
1.502(2), C(1)–C(10) 1.522(3) Å. Selected valence angles: C(4)–C(3)–C(2) 116.83(16), C(1)–C(3)–C(2)
57.60(12), C(2)–C(4)–C(3) 60.12(12), C(1)–C(2)–C(3) 62.29(12)º. The full crystallographic data for compound
10b has been placed in the Cambridge Crystallographic Centre Database (reference CCDC 657427).
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