Synthesis and characterization of (Z)-1-[2-(tribenzylstannyl)vinyl]-1-cycloheptanol and its benzylhalostannyl derivatives

Article abstract of DOI:10.1081/SIM-120021941

1-Ethynyl-1-cycloheptanol reacts with tribenzylstannylhydride, (C₆H₅CH₂)₃SnH, and generates the corresponding (Z)-1-[2-(tribenzylstannyl)vinyl]-1-cycloheptanol. The product obtained reacts with one or two equivalents of halogen (I₂, Br₂ or ICl) to form the associated (Z)-1-[2-(dibenzylhalostannyl)vinyl]-1-cycloheptanol or (Z)-1-[2-(benzyldihalostannyl)-vinyl]-1-cycloheptanol, respectively. All compounds were characterized by elemental analyses, IR, ¹H NMR. The X-ray diffraction analysis of (Z)-1-[2-(tribenzylstannyl)vinyl]-1-cycloheptanol shows the presence of an intramolecular coordination of oxygen to the tin atom giving rise to a five-membered ring in which the metal exhibits a distorted trigonal-bipyramidal geometry. This may explain that a benzyl group, probably the apical one, is cleaved more easily by halogen than the vinyl substituent.

Full text of DOI:10.1081/SIM-120021941

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Synthesis and Characterization of
(Z)‐1‐[2‐(Tribenzylstannyl)vinyl]‐1‐cycloheptanol and
its Benzylhalostannyl Derivatives
Yujie Ren a , Cuiying Jia a , Peng Liang a , Xuefeng Yang a & Huilin Chen b
a Chemistry Department , Dalian University of Technology , Dalian, 116024, P.R. China
b Dalian Institute of Chemical Physics , The Chinese Academy of Science , Dalian, 116023,
P.R. China
Published online: 15 Feb 2007.
To cite this article: Yujie Ren , Cuiying Jia , Peng Liang , Xuefeng Yang & Huilin Chen (2003) Synthesis and Characterization of
(Z)‐1‐[2‐(Tribenzylstannyl)vinyl]‐1‐cycloheptanol and its Benzylhalostannyl Derivatives, Synthesis and Reactivity in Inorganic
and Metal-Organic Chemistry, 33:6, 1115-1123
To link to this article: http://dx.doi.org/10.1081/SIM-120021941
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SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY
Vol. 33, No. 6, pp. 1115–1123, 2003
Synthesis and Characterization of
(Z)-1-[2-(Tribenzylstannyl)vinyl]-1-cycloheptanol
and Its Benzylhalostannyl Derivatives
1
1
Yujie Ren,1, Cuiying Jia, Peng Liang,
*
Xuefeng Yang,1 and Huilin Chen2
1Chemistry Department, Dalian University of Technology,
Dalian, P.R. China
2Dalian Institute of Chemical Physics, The Chinese Academy of Science,
Dalian, P.R. China
ABSTRACT
1-Ethynyl-1-cycloheptanol reacts with tribenzylstannylhydride,
(C6H5CH2)3SnH, and generates the corresponding (Z)-1-[2-(tribenzyl-
stannyl)vinyl]-1-cycloheptanol. The product obtained reacts with one or
two equivalents of halogen (I2, Br2 or ICl) to form the associated (Z)-1-
[2-(dibenzylhalostannyl)vinyl]-1-cycloheptanol or (Z)-1-[2-(benzyldiha-
lostannyl)-vinyl]-1-cycloheptanol, respectively. All compounds were
characterized by elemental analyses, IR, 1H NMR. The X-ray diffraction
analysis of (Z)-1-[2-(tribenzylstannyl)vinyl]-1-cycloheptanol shows the
presence of an intramolecular coordination of oxygen to the tin atom
*
Correspondence: Yujie Ren, Chemistry Department, Dalian University of Tech-
nology, Dalian 116024, P.R. China; E-mail: yujie_ren@163.com.
1115
DOI: 10.1081/SIM-120021941
0094-5714 (Print); 1532-2440 (Online)
www.dekker.com
Copyright D 2003 by Marcel Dekker, Inc.

1116
Ren et al.
giving rise to a five-membered ring in which the metal exhibits a
distorted trigonal-bipyramidal geometry. This may explain that a benzyl
group, probably the apical one, is cleaved more easily by halogen than
the vinyl substituent.
Key Words: Synthesis; Characterization; Organotin compound.
INTRODUCTION
It has been reported[1] that Ph3SnH adds to 17-ethynyl-4-estren-17b-ol
to give (Z)-17-[2-(triphenylstannyl)vinyl]-4-estren-17b-ol. This triphenyl-
vinyltin derivative reacts smoothly with one or two equivalents of iodine,
leading exclusively to the cleavage of one or two phenyl-tin bonds, res-
pectively. A 1:1 molar ratio gives rise to (Z)-17-[2-(iododi-phenylstannyl)-
vinyl]-4-estren-17b-ol, a 2:1 molar ratio, (Z)-17-[2-(diiodophenylstannyl)-
vinyl]-4-estren-17b-ol, which exhibits interesting antitumour activities.[2]
Thus, the vinyl-tin bond is not cleaved at all. The intramolecular co-
ordination bond from oxygen to tin in this compound is likely to be re-
sponsible for this high regioselectivity in the phenyl-tin bond cleavage.
In order to check the general validity of this assumption, we prepared
model compounds in which the same intramolecular coordination bond is
present, giving rise to the same cyclic, tin-containing unit, but without
the steroid moiety of (Z)-17-[2-(triphenylstannyl)vinyl]-4-estren-17b-ol.[1]
Moreover, we examined the influence of benzyl substitution on the phenyl
ring in order to find out whether this modification induces a noticeable
change in the reactivity with iodine. We synthesized (Z)-1-[2-(tribenzyl-
stannyl)vinyl]-1-cycloheptanol and corresponding mono-and dihalides.
EXPERIMENTAL
Materials
1-Ethynyl-1-cycloheptanol was prepared according to Verkruijsse
et al.,[3] b.p 81–83 ꢀC/26 mm Hg; yield: 47%. Tribenzyltin hydride was
prepared according to the procedure of Kuivila et al.,[4] mp 102–104 ꢀC,
yield: 45%, n(Sn–H): 1835 cm–1, and was directly used without seperation.
Physical Measurements
IR spectra were recorded on a Nicolet 360 FT-IR spectrometer, 1H
NMR spectra were obtained on a Varian Unity-400 NMR spectrometer at

(Z)-1-[2-(Tribenzylstannyl)vinyl]-1-cycloheptanol
1117
400 MHz proton resonance frequency. The chemical shifts of the proton
NMR spectra are reported with TMS as internal standard and CDCl3 as
solvent. The elemental analysis data for C and H were obtaind on a PE
2400 C–H–N automatic element analyzer. The content of Sn was deter-
mined on a VRA-20 X-ray fluorescence spectrometer.
Synthesis of (Z)-1-[2-(Tribenzylstannyl)vinyl]-
1-cycloheptanol (1)
Tribenzyltin hydride (15.74 g, 40 mmol) and 1-ethynyl-1-cycloheptanol
(5.56 g, 40 mmol) were placed into a two-necked flask equipped with a
condenser on top of which was placed a CaCl2 tube. 30 mL of diethyl ether
and 20 mg of dibenzoyl peroxide were added to this mixture which was
kept under nitrogen. After magnetic stirring for 20 h, diethyl ether was
evaporated and the residue was recrystallized from ethanol, The main
product (Z)-1-[2-(tribenzylstannyl)vinyl]-1-cycloheptanol (1) was obtained
in 55.4% (11.77 g) yield; mp 74–75 ꢀC. Anal. Calcd. for C30H36OSn (531):
C, 67.79; H, 6.78; Sn, 22.41%. Found: C, 67.35; H, 6.65; Sn, 22.61%. IR
(KBr), nmax cm–1: 3571.7 (s, OH), 1084.0 (s, CO), 529.0 (Sn O). 1H
NMR (CDCl3) d ppm: 0.67 (1H, s, OH), 1.54 (12H, br, C7H12), 2.28 (6H, s,
3CH2), 5.55 (d, J = 13 Hz, = CH À cycloheptyl), 6.58 (d, J = 13 Hz,
CH À Sn), 6.83–7.17 (15H, m, 3C6H5). Hexabenzylditin, obtained as an
insoluble byproduct, was filtered off; 11.2% (3.5 g) yield.
Synthesis of (Z)-1-[2-(Dibenzylhalostannyl)vinyl]-
1-cycloheptanols (2), (3) and (4) and (Z)-
1-[2-(Benzyldihalostannyl)vinyl]-
1-cycloheptanols (5), (6), and (7)
Typically, a solution of 1.6 g (10 mmol) of Br2 in 100 mL of CCl4 was
added drop-wise under magnetic stirring to a solution of 5.3 g (10 mmol)
of (1) in 100 mL of the same solvent. The color of Br2 disappeared im-
mediately. After having added the last drop of bromine a colorless solution
was obtained. The reaction mixture was kept for 4 h at room temperature;
then the solvent was evaporated. The residue was recrystallized from cy-
clohexane. A solid, (Z)-1-[2-(dibenzylbromostannyl)vinyl]-1-cycloheptanol
(3), was obtained in 71.2% (3.69 g) yield.
Analogous procedures were used for the synthesis of compounds (2)
and (4)–(7).
(2) Yellow pasty compound, yield 54.1%. Anal. Calcd. for C23H29IOSn
(567): C, 48.68; H, 5.11; Sn, 20.99%. Found: C, 48.26; H, 5.10; Sn, 20.88%.
1
IR (KBr), nmax cm–1: 3416.7 (s, OH), 1041.3 (s, CO), 526.0 (Sn O). H
NMR (CDCl3) d ppm: 2.24 (1H, s, OH), 1.53 (12H, br, C7H12), 2.28 (4H, s,

1118
Ren et al.
2CH2), 6.37 (d, J = 12 Hz, =CH À cycloheptyl), 6.81 (d, J = 12 Hz,=CH À
Sn), 6.73–7.21 (15H, m, 3C6H5).
(3) Colorless solid, yield 71.2%, mp 106–108 ꢀC. Anal. Calcd. for
C23H29BrOSn (520): C, 53.08; H, 5.58; Sn, 22.88%. Found: C, 53.01; H,
5.46; Sn, 22.68%. IR (KBr), nmax cm–1: 3403.6 (s, OH), 1050.4 (s, CO),
1
535.0 (Sn O). H NMR (CDCl3) d ppm: 2.35 (1H, s, OH), 1.53 (12H, br,
C7H12), 2.28 (4H, s, 2CH2), 6.31 (d, J=12 Hz, =CH–cycloheptyl), 6.89 (d,
J = 12 Hz, =CH À Sn), 6.83–7.17 (15H, m, 3C6H5).
(4) Colorless solid, yield 81.2%, mp 145–146 ꢀC. Anal. Calcd. for
C23H29ClOSn (475.5): C, 58.04; H, 6.10; Sn, 25.03%. Found: C, 58.00; H,
6.01; Sn, 24.98%. IR (KBr), nmax cm–1: 3411.0 (s, OH), 1051.3 (s, CO),
1
520.0 (Sn O). H NMR (CDCl3) d ppm: 2.41 (1H, s, OH), 1.54 (12H, br,
C7H12), 2.28 (4H, s, CH2), 6.26 (d, J = 12 Hz, =CH–cycloheptyl), 6.92 (d,
J = 12 Hz, =CH À Sn), 6.70–7.28 (15H, m, 3C6H5).
(5) Colorless solid, yield 60.1%, mp 64–66 ꢀC. Anal. Calcd. for
C16H22I2OSn. (603): C, 31.88; H, 3.68; Sn, 19.69%. Found: C, 31.82; H,
3.63; Sn, 19.68%. IR (KBr), nmax cm–1: 3420.6 (s, OH), 1048.1 (s, CO),
1
520.0 (Sn O). H NMR (CDCl3) d ppm: 2.54 (1H, s, OH), 1.62 (12H, br,
C7H12), 2.28 (2H, s, CH2), 6.40 (d, J = 10 Hz, =CH–cycloheptyl), 6.64 (d,
J = 10 Hz, =CH À Sn), 6.80–7.17 (15H, m, 3C6H5).
(6) Colorless solid, yield 81.8%, mp 152–154 ꢀC. Anal. Calcd. for
C16H22Br2OSn. (509): C, 37.76; H, 4.36; Sn, 23.33%. Found: C, 37.72; H,
4.31; Sn, 23.29%. IR (KBr), nmax cm–1: 3417.2 (s, OH), 1054.6 (s, CO),
1
539.0 (Sn O). H NMR (CDCl3) d ppm: 2.89 (1H, s, OH), 1.63 (12H, br,
C7H12), 2.28 (2H, s, CH2), 6.33 (d, J = 10 Hz, =CH–cycloheptyl), 6.89 (d,
J=10 Hz, =CH À Sn), 6.79–7.27 (15H, m, 3C6H5).
(7) Colorless solid, yield 85.8%, mp 144–145 ꢀC. Anal. Calcd. for
C16H22Cl2OSn. (420): C, 45.76; H, 5.28; Sn, 28.27%. Found: C, 45.71; H,
1
5.20; Sn, 28.23%. nmax: 3411.1 (s, OH), 1054.9 (s, CO), 529.0 (Sn O). H
NMR (CDCl3) d ppm: 3.20 (1H, s, OH), 1.61 (12H, br, C7H12), 2.28 (2H, s,
CH2), 6.26 (d, J = 10 Hz, =CH À cycloheptyl), 6.98 (d, J = 10 Hz,
CH À Sn), 6.83–7.17 (15H, m, 3C6H5).
X-Ray Structure Determination of Compound (1)
A crystal, dimensions 0.15 mm  0.25 mm  0.50 mm, was used to
collect data on a MAC DIP-2030K automatic diffractometer. The structure
of (Z)-1-[2-(tribenzylstannyl)-vinyl]-1-cycloheptanol (1) has been deter-
mined by X-ray diffraction analysis and is shown in Figure 1. Unit cell
˚
dimensions a = 9.474(1), b = 25.858(2), c=10.717(1) A, b =92.988(4)ꢀ,
3
V = 2621.9(3) A , Z = 4, Dc = 1.346 g.cm–3. Data were collected by the o
˚

(Z)-1-[2-(Tribenzylstannyl)vinyl]-1-cycloheptanol
1119
Figure 1. Structure of compound (1).
scan technique with 2qꢀ 50.0ꢀ. During data collection no decay was found.
The intensities were corrected for Lorentz, polarization and absorption
effects [m(M0 Ka) = 10.48 cm–1]. The scan range was 0–180ꢀ. Calculations
were carried out with the SHELXS-86 system of computer programs.
Systematic absences showed the space group to be p21/c. The position of the
tin atom and all the non-hydrogen atoms was determined from a three
dimensional Patterson map followed by the use of Fourier technique. They
were refined anisotropically by least-squares methods and the positions of all
the hydrogen atoms could be located from geometric and difference Fourier
2
2
calculations. Final R = 0.079 for 3631 observed reflections (jFj ꢁ 8s jFj )
2
Rw = 0.075, w = 1/sjFj .
RESULTS AND DISCUSSION
Synthesis
The (Z)-1-[2-(tribenzylstannyl)vinyl]-1-cycloheptanol (1) was synthe-
sized by the addition of tribenzyltin hydride to the triple bond of 1-ethynyl-
1-cycloheptanol (Eq. 1).

1120
Ren et al.
The reactions of (1) with halogens in a 1:1 or 1:2 molar ratio yield the
corresponding mono- and di-halides (2)–(7), respectively (Eqs. 2 and 3).
ð1Þ
ð2Þ
ð3Þ
The reaction conditions are described in Table 1. The physical pro-
perties of the new products are described in the experimental details.
Table 1. Reaction conditions and recrystallization solvents during the synthesis of
compounds (2) to (7).
Starting
Molar
Reaction Reaction Recrystallization
solvent
compound Halogen ratio Product time (h) temp (°C)
(1)
(1)
(1)
I2
1:1
1:1
1:1
(2)
(3)
(4)
6
4
4
18
À 10
À 5
cyclohexane
cyclohexane
cyclohexane/
Br2
ICl
a
CCl4
cyclohexane/
(1)
I2
1:2
(5)
48
À 10
a
CCl4
cyclohexane
cyclohexane/
(1)
(1)
Br2
ICl
1:2
1:2
(6)
(7)
10
8
À 10
0
a
CCl4
a1:1, v/v.

(Z)-1-[2-(Tribenzylstannyl)vinyl]-1-cycloheptanol
1H NMR Spectra
1121
The proton NMR spectrum of compound (1), obtained after the ad-
dition of one equivalent of tribenzyltin hydride to the triple bond of 1-
ethynyl-1-cycloheptanol, no longer exhibits the signal of the acetylenic
proton at 2.55 ppm, characteristic of the starting material. Rather, com-
pound (1) shows characteristic ethylenic proton signals at 5.55 and 6.58
3
ppm, namely two doublets with JHC=CH = 13 Hz.
When compound (1) reacts with one equivalent of halogen, the vinylic
protons appear at 6.37 and 6.81 ppm (2); 6.31 and 6.89 ppm (3); 6.26 and
3
6.92 ppm (4), respectively, again as doublets JHC=CH = 12 Hz. The pre-
sence of vinylic protons clearly shows that the benzyl-tin bond is cleaved by
halogen and the –CH=CH–Sn bond remains intact. Indeed, no other signals
from the vinylic –CH=CH–X (X = Cl; Br; I) protons could be detected in
the proton NMR spectrum. Therefore, compounds (2)–(4) were identified as
(Z)-1-[2-(dibenzylhalo-stannyl)vinyl]-1-cycloheptanol.
After the addition of a second equivalent of halogen, the vinylic pro-
tons change to 6.40 and 6.64 ppm (5); 6.33 and 6.89 ppm (6); 6.26 and
3
6.98 ppm (7) as doublets JHC=CH = 10 Hz. This shows that the second
group cleaved by halogen is again a benzyl group, thus, compounds (5)–(7)
are (Z)-1-[2-(benzyldihalostannyl) vinyl]-1-cycloheptanols.
In addition, we have separated the side product benzyl bromide, and
1
1
have obtained its H NMR spectrum, it showed the correct data for the H
NMR spectrum of benzyl bromide.
3
The coupling constant JHC = CH = 13 Hz observed for compound (1) is
rather larger than cis coupling constants in five-membered rings which
usually amount to 8 Hz or even less. However, this ring, containing a tin
˚
Table 2. Selected bond lengths (A) and angles (ꢀ).
O(1)–Sn
Sn(1)–C(10)
2.728(1)
2.174(10)
2.176(9)
1.521(13)
1.324(13)
1.534(13)
114.5(4)
116.4(3)
109.8(4)
Sn(1)–C(9)
Sn(1)–C(10@)
O(1)–C(1)
2.153(9)
2.176(9)
1.456(11)
1.532(16)
1.492(14)
1.478(12)
103.8(4)
105.8(4)
105.4(4)
Sn(1)–C(10’)
C(1)–C(8)
C(8)–C(9)
C(2)–C(3)
C(10)–C(11)
C(10’)–C(11’)
C(9)–Sn(1)–C(10)
C(9)–Sn(1)–C(10@)
C(10)–Sn(1)–C(10@)
C(10@)–C(11@)
C(9)–Sn(1)–C(10’)
C(10)–Sn(1)–C(10’)
C(10’)–Sn(1)–C(10@)

1122
Ren et al.
atom, is characterized by rather abnormal bond angles. This coupling
constant decreases from compound (1) to compound (7).
Molecular Structure of Compound (1)
The structure of compound (1) has been determined by X-ray diff-
raction and is shown in Figure 1. As shown in Figure 1, compound (1) has
a distorted trigonal bipyramidal geometry which is similar to that of (Z)-17-
[2-(triphenylstannyl)vinyl]-4-estren-17b-ol.[1] Selected bond lengths and
angles are given in Table 2.
The central tin atom has a strongly distorted trigonal-bipyramidal geo-
metry with O and C(10’) atoms in apical positions and the C(9), C(10) and
C(10@) atoms in equatorial positions. Even if we do not take into account
the tin-oxygen interaction, a tetrahedral environment around tin is not
credible because the angles C(9)–Sn–C(10) (114.5ꢀ) and C(9)–Sn–C(10@)
(116.4ꢀ) indicate a distorted trigonal-bipyramidal geometry. The fact that
the Z isomer is obtained rather than the E isomer generally formed in this
type of reaction might be attributed to the intramolecular O ! Sn coordi-
nation observed experimentally.
ACKNOWLEDGMENT
This project was supported by the Dalian University of Technology
Innovate Foundation.
REFERENCES
1. Pan, H.D.; Willem, R.; Meuier-Piret, J.; Gielen, M. Intramolecular
O ! Sn Coordination in (Z)-17-[2-(triphennylstannyl)vinyl]-4-estren-
17-ol: evidence by X-ray diffraction analysis and iodo demetalation.
Organometallics 1990, 9, 2199–2201.
2. Eur. Patent 90202936-2, June 11, 1990, Gielen, M.; Huade, P.; Willem,
R.; De Vos, D. Antitumor composition and compounds, Chem. Abstr.
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(Z)-1-[2-(Tribenzylstannyl)vinyl]-1-cycloheptanol
1123
ketones with organotin hydrides. J. Am. Chem. Soc. 1961, 83, 1246–
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Received October 16, 2002
Accepted March 10, 2003
Referee I: M. Ehses
Referee II: A. Rammo