Novel amino propyl substituted organo tin compounds

Article abstract of DOI:10.1139/cjc-2013-0504

In this work, a new synthetic pathway yielding unprotected amino propyl tin compounds is described.For this purpose, mono stannanes with different substitution patterns are used.In a first step, tin hydrides are deprotonated using lithium diisopropyl amide and mixed with an electrophile containing a protected amine in the cω;-position.After deprotection via acidic hydrolysis, the desired amino propyl tin compounds are obtained in high yield and purity.The thermal reaction behavior of the amino propyl tin hydrohalide intermediates containing one aromatic residue at the central tin atom is also investigated.For this purpose, amino propyl tin hydrohalides are heated under vacuum until the aromatic hydrocarbon is liberated.This thermal treatment leads to so far unknown tin halides containing an amino propyl side chain.For all of these substances detailed liquid ¹H, ¹³C, and ¹¹⁹Sn-nuclear magnetic resonance (NMR) data were obtained, and in one case solid state NMR is also conducted.Regarding solids, single crystal X-ray analysis is performed.Some derivatization reactions with these new substances are demonstrated, especially the synthesis of an amino propyl tin carboxylate, which might be very interesting for biological, pharmaceutical, or technical processes.

Full text of DOI:10.1139/cjc-2013-0504

565
ARTICLE
Novel amino propyl substituted organo tin compounds
Johann Pichler, Ana Torvisco, Patrick Bottke, Martin Wilkening, and Frank Uhlig
Abstract: In this work, a new synthetic pathway yielding unprotected amino propyl tin compounds is described. For this
purpose, mono stannanes with different substitution patterns are used. In a first step, tin hydrides are deprotonated using
lithium diisopropyl amide and mixed with an electrophile containing a protected amine in the ␻-position. After deprotection via
acidic hydrolysis, the desired amino propyl tin compounds are obtained in high yield and purity. The thermal reaction behavior
of the amino propyl tin hydrohalide intermediates containing one aromatic residue at the central tin atom is also investigated.
For this purpose, amino propyl tin hydrohalides are heated under vacuum until the aromatic hydrocarbon is liberated. This
thermal treatment leads to so far unknown tin halides containing an amino propyl side chain. For all of these substances detailed
liquid 1H, 13C, and 119Sn-nuclear magnetic resonance (NMR) data were obtained, and in one case solid state NMR is also conducted.
Regarding solids, single crystal X-ray analysis is performed. Some derivatization reactions with these new substances are
demonstrated, especially the synthesis of an amino propyl tin carboxylate, which might be very interesting for biological,
pharmaceutical, or technical processes.
Key words: organotin, aminopropyl, protecting group, monostannane, solution and solid sate solid-state NMR study.
Résumé : Cette étude décrit une nouvelle voie de synthèse conduisant a` la formation de composés d’aminopropylétain non
protégés. On utilise pour cela des monostannanes selon différents modes de substitution. Dans un premier temps, ces hydrures
d’étain sont déprotonés au moyen du diisopropylamidure de lithium et mélangés avec un électrophile comportant une amine
protégée en position ␻. Après déprotection par hydrolyse acide, les composés d’aminopropylétain désirés sont obtenus avec un
rendement et une pureté élevés. Le comportement thermoréactif des hydrohalogénures d’aminopropylétain intermédiaires, qui
contiennent un résidu aromatique situé sur l’atome d’étain central, a été également étudié. Pour cela, les hydrohalogénures
d’aminopropylétain sont chauffés sous vide jusqu’a` ce que l’hydrocarbure aromatique soit libéré. Ce traitement thermique
conduit a` la formation d’halogénures d’étain, inconnus jusqu’a` aujourd’hui, comportant une chaîne latérale aminopropylique.
Pour toutes ces substances, des données détaillées ont été obtenus par résonnance magnétique nucléaire (RMN) 1H, 13C et 119Sn,
en phase liquide. Une analyse par RMN a` l’état solide a été également réalisée pour l’une des substances étudiées. Dans le cas de
solides, une analyse par cristallographie aux rayons X a été effectuée. Certaines réactions de dérivatisation avec ces nouvelles
substances sont mises en évidence, en particulier la synthèse d’un carboxylate d’aminopropylétain dont l’application a` des
procédés biologiques, pharmaceutiques ou techniques pourrait s’avérer intéressante. [Traduit par la Rédaction]
Mots-clés : organoétain, aminopropyle, groupe protecteur, monostannane, étude par RMN en solution et a` l’état solide.
show that hexakis(␥-aminopropyl)ditin and tetrakis(␥-aminopropyl)tin
Introduction
as fully aminopropylated derivatives were accessible in 1967.14,15
In organosilicon chemistry, compounds with amino propyl groups
In 1979, Weichmann described the synthesis and derivatization of
are very well known (e.g., AMMO (3-(trimethoxysilyl)propane-1-amine),
AMEO (3-(triethoxysilyl)propane-1-amine), AAMS (N-(2-aminoethyl)-
3-aminopropyltrimethoxysilane)). They are commonly used for
amino ethyltin compounds.16 Different aryl and alkyl substitu-
ents on the tin atom were used, and also typical derivatization
reactions with the amino nitrogen were demonstrated. However,
so-called silyl-terminated polyurethanes (STPU) in modern con-
no further investigations were performed on any of these com-
struction.1–9 However, much less is known about compounds that
pounds. This is perhaps due to the drawbacks of the synthetic
involve the heavier group 14 elements. For this reason, we decided
procedures used so far. The compounds synthesized by Gilman,
to investigate organo-tin compounds containing amino propyl
Lequan, and later on also by Jurkschat and co-workers17 were
groups. These types of substances should provide new applica-
made via simple salt-elimination reactions, but it was impossible
tions in polymer science, catalysis, and biological activity. The
first attempts to synthesize such compounds were made in 1955
by Gilman, who described the synthesis of triphenyl-␥-N,N-
diethylaminopropyltin.10 Twenty years later, a N,N-dimethylamino
derivative was synthesized by Lequan.11 Van der Kerk succeeded in
the synthesis of triphenylaminopropyltin as the first real amino
propyl compound, also checking for antifungal properties of this
substance.12,13 Using an electrochemical procedure, Smith was able to
to remove the substituents from the nitrogen afterwards, and
thus no further reactions were possible, with the exception of
quarternization,10 salt-formation,18 and possibly oxidation lead-
ing to N-oxides. Van der Kerk established a hydrostannylation
reaction with unsaturated hydrocarbons to form the tin carbon
bond.12 Unfortunately, this reaction gives different regioisomers
of the desired product, and in addition only activated double
bonds (e.g., acrylnitrile, allylacetate) tend to react with the Sn–H
Received 31 October 2013. Accepted 5 February 2014.
J. Pichler, A. Torvisco, and F. Uhlig. Institut für Anorganische Chemie, Graz University of Technology, Stremayrgasse 9/IV, 8010 Graz, Austria.
P. Bottke and M. Wilkening. Institute for Chemistry and Technology of Materials, Graz University of Technology, Stremayrgasse 9, 8010 Graz, Austria.
Corresponding author: Frank Uhlig (e-mail: frank.uhlig@tugraz.at).
This article is part of a Special Issue commemorating the 14th International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin, and Lead
(ICCOC-GTL 2013) held in Baddeck, NS, July 2013.
Can. J. Chem. 92: 565–573 (2014) dx.doi.org/10.1139/cjc-2013-0504
Published at www.nrcresearchpress.com/cjc on 25 February 2014.

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Can. J. Chem. Vol. 92, 2014
Scheme 1. Alkylation of (E)-N-(3-chloropropyl)-2,2-dimethylpropan-1-imine (1) with lithium stannides.
R2
Sn
R3
R2
Sn
R3
R1
Li
R1
THF, 0 °C
-LiCl
N
Cl
N
2-4
1
R1, R2, R3 = Alkyl, Aryl
R1 R2 R3
2 = Ph Ph Ph
3 = Ph Ph nPr
4 = Ph Et
Et
moiety, as shown by our own experiments19 as well as by Pham.20
The electrochemical approach of Smith leads to product mix-
tures and only persubstituted tin compounds, which are also
not desirable since introduction of other substituents at the tin
atom is difficult.15 Finally, the C2-spacer in Weichmann’s pro-
cedure16 tends to undergo Grob-fragmentation21 even at low
temperatures, thus the practical use of these compounds is
limited. Therefore, we decided to investigate a new approach
for the synthesis of such amino propyl tin compounds. We also
studied the thermochemical properties of our compounds in com-
parison with those of Weichmann.16 Finally, we also demonstrate
some derivatization reactions on these new substances.
detected, and only the desired salt elimination occurs, leading to
usually pure products according to 1H-NMR in yields >90%, with-
out any purification steps being necessary. The crucial step of
deprotection was easily achieved by using diluted aqueous solu-
tions of HCl in equimolar amounts. By doing so, the imine is
hydrolyzed, and the liberated aldehyde was removed together
with the water under vacuum. The labile Sn–C bond remains
untouched under these conditions and leads to an almost quanti-
tative transformation into the corresponding aminopropyltin
hydrochlorides, which can be isolated as an oily liquid (9) or amor-
phous solids (5, 7). However, if concentrated HCl is used for the
deprotection reaction chlorination at the tin atom also occurs. As
the final step, the aminopropyltin compound is liberated from
its hydrochloride by subsequent treatment with an equimolar
amount of KOH in MeOH, followed be evaporation of the solvent
and extraction of the product with CH2Cl2 (Scheme 2).
Results and discussion
For the synthesis of the desired amino propyltin compound
(2–4) using our procedure, the nucleophilic tin species needs to be
generated first. Different procedures for the generation of nuce-
lophilic tin species are given in the literature. In the simplest case,
triorganotin halides are treated with alkali metals22 in ethereal
solvents or hexaorgano-distannanes with alkali metals,23 or or-
gano lithium reagents23 in ethers. This strategy usually requires
reaction times up to 48 h with reflux. In many cases, naphthalene
is needed as a catalyst in amounts up to 10 mol%. If different
substituents are present at the tin atom, these harsh conditions
and long reaction times lead to product mixtures via exchange
reactions of the organic residues at the tin atoms.24 In fact, only in
the case of Ph6Sn2 is this reaction suitable for the generation of
anionic tin species, since the reaction proceeds within 4 h without
any catalyst and gives only one product instead of inseparable
product mixtures. In contrast to the aforementioned procedure,
the deprotonation of tin hydrides is an alternative route. Since
pure tin hydrides can easily be synthesized25,26 and the deproto-
nation reaction is a very fast reaction, product mixtures can be
avoided. For this task, different reagents are mentioned in the
literature and mostly all strong bases can be used.27–29 However,
lithium diisopropyl amide (LDA) was shown to be the reagent of
choice for this reaction, since it is commercially available, easy to
handle, and leads to excellent stannide yields even in cases where
other reagents failed completely.30,31 Tin hydrides (16–18) treated
with LDA at 0 °C give yellow to red solutions of the desired anion.
These solutions are stable at this temperature for several hours.
To avoid side reactions, the solutions are used immediately after
preparation. The stannide solution is then added to the electrophile,
which already contains the amino group synthon (Scheme 1).
According to 1H-NMR, the yields of clean product (6, 8, 10) are
again almost quantitative, which can be easily accomplished by
recrystallization or distillation if necessary. Weichmann16 re-
ported that heating of his aminoethyltin hydrohalides leads to the
liberation of ethane and the nitrogen residue via a Grob type frag-
mentation21 (Scheme 3) instead of a the expected protodearylation
reaction at the tin atom.
For this reason we also investigated the thermal reactivity of
the aminopropyltin hydrohalides. Hydrochloride (11), -bromide
(12), and -iodide (13) derivatives of 10 were synthesized by aque-
ous hydrolysis of 4 with the desired aqueous hydrohalide acid. The
diethylphenyl substitution pattern was chosen to suppress rear-
rangement reactions as well as oligo substitution at the tin atom,
so that in an ideal case only Grob fragmentation and (or)
protodearylation of the phenyl group could occur (Scheme 4).
Initially, compound 4 was treated with diluted HCl to yield the
corresponding hydrochloride 9. TGA/DSC/MS measurements were
conducted on this substance to examine its thermal stability and
to detect possible reaction products. According to these measure-
ments, an exothermic decomposition reaction takes place be-
tween 120 and 150 °C, which is in the same region as stated in
Weichmann’s paper,16 but in contrast to his findings, in our case
benzene is liberated leading to 3-(chlorodiethylstannyl)propan-1-
amine (11). To prove these findings, the thermal treatment of 9
was repeated in a preparative scale. In this case, the hydrochloride
9 was placed in a Schlenk tube equipped with a reflux condenser.
While heating under vacuum, benzene was eliminated first, and
the product distilled into the condenser at ϳ250 °C where it so-
lidified. The solid residue was then recrystallized out of benzene
to yield pure 11. In the same way, the bromo- and iodo-derivatives
(12 and 13) were also synthesized but without isolation of the
hydrohalide intermediate. Compound 11 was converted by a salt
metathesis into the fluoro-derivative 14 via reaction with KF in
THF/acetone and into the corresponding acetate 15 with sodium
acetate in methanol. However, for the synthesis of 14, the addi-
tion of acetone in this Finkelstein type reaction could not be
avoided, thus leading to formation of the corresponding acetone
ketimine as a major side product (ϳ40% according to 19F-NMR) and
lowering the yield of the whole reaction compared with the syn-
thesis of (15). We tried to perform single crystal analysis on all
Since the commercially available ␣,␻-chloroaminopropyl hy-
drochloride contains active hydrogen, a protection group is nec-
essary to avoid unwanted side reactions. Unfortunately, protection
groups for amino groups, which are commonly used in organic
chemistry, cannot be used in this case,32 since, most likely, the
reaction conditions for the deprotection step would also break the
tin–carbon bonds within the molecule. Therefore, we introduced
the imino derivative 1, which enables us to synthesize our target
compounds in very high yields. Compound 1 is completely stable
under the basic conditions of the coupling reaction with the tin
anion. Thus, neither elimination reactions at the chlorine carbon
nor nucleophilic attack at the carbonyl analog imino carbon was
Published by NRC Research Press

Pichler et al.
567
Scheme 2. Deprotection of aminopropyltin compounds via acidic hydrolysis.
R2
Sn
R3
R2
Sn
R3
R2
Sn
R3
R1
R1
R1
0.1M HCl
KOH/MeOH
- KCl
N
NH2*HCl
NH2
-
O
R1, R2, R3 = Alkyl, Aryl
R1 R2 R3
6 = Ph Ph Ph
8 = Ph Ph nPr
R1 R2 R3
5 = Ph Ph Ph
7 = Ph Ph nPr
10 = Ph Et
Et
9 = Ph Et
Et
Scheme 3. Grob fragmentation of aminoethyltin hydrochloride compounds.
Scheme 4. Thermally induced protodearylation of aminopropyltin hydrohalides and substitution reactions.
R1
Sn
R2
R1
Sn
R2
H
N
Ar
Ar
0.1 M HX
N
-
H
H
X
O
4
10
R1
Sn
R2
H
N
R1
Sn
R2
H
N
R2
H
N
Ar
X
Y
Δ
MY
Sn
R3
-MX
-ArH
H
H
H
H
X
11-13
X = Cl, Br, I
14,15
Y = F, OAc
R1, R2 = Alkyl, Aryl
Ar = Ph; R1 = R2 = Et
10 : X = Cl
11 : X = Cl
12 : X = Br
13 : X = I
14 : X = F
15 : X = OAc
solid products in this investigation. However, in the case of the
synthesized hydrohalides, it was not possible to grow suitable
crystals even after several attempts of recrystallization. For the
other solid compounds (6, 11–15), full X-ray data are provided. We
also succeeded in the crystallization and mounting of the low
melting point starting material triphenylstannane (16) (Fig. 1) as a
rare example of a crystalline stannane.
with an electronegative substituent, the environment around the
tin atom changes dramatically. Also in Fig. 2, the iodo compound
13 is shown as a demonstrating example for comparison. For all
the similar derivatives (11–15) stated in this paper, important
bond lengths and angles can be found in Table 2.
In all these cases, the central tin atom is surrounded by a
trigonal-bipyramidal environment with the electronegative sub-
stituents in apical positions. Interestingly, the Sn–N bond dis-
tances are of similar lengths (Table 2). The shortest Sn–N bond
length is found in the iodo compound 13 with 2.330(3) Å, while the
longest is 2.397(2) Å for the acetate 15. For the halogen substitu-
ents (F, Cl, Br, I), the Sn–X bond length increases as the size of the
halogen atom increases. The shortest bond length is found for
fluoride 14 with 2.108(1) Å compared with 3.060(3) Å for the iodide
13. Within this homologous row, the compounds crystallize in a
different manner. Fluoride 14 and chloride 11, as well as the ace-
tate 15, are found in a P21/n space group in the monoclinic crystal
lattice, whereas bromide 12 and iodide 13 are in the Pbca space
group in the orthorhombic crystal lattice (Table 1). This might be
due to two different supramolecular structures found for these
substances. With the most electronegative elements (F, O, Cl),
compared to Br and I, a different polymeric structure is formed by
H-X interactions. For the first case, the supramolecular lattice of
the chloro compound 11 is shown as an example and the iodo
derivative 13 for the second case (Fig. 3).
In fact there are only two other examples known in the litera-
ture, both reported by our group. For 16, the hydrogen at the tin
atom was located in the difference map, and thus we are able to
provide the first experimental Sn–H bond length (1.13(5) Å) mea-
surement for monostannanes. However, it is not possible to com-
pare the Sn–H bond length of 16 with the only other known tin
monohydrides. In the case of 2,6-xylyl3SnH,34 the Sn–H was not
reliably located in the difference map, which is a common prob-
lem with light atoms (hydrogen) located next to heavy atoms
33
because of their poor scattering abilities. For mesityl2SnH2,
which is a dihydride, Sn–H bonds are in the average of 1.669(2) Å.
The solid structure of 16 also shows interesting secondary inter-
actions between a hydrogen atom of one aromatic ring forming
an edge to face interaction (2.778 Å) with one of the phenyl sub-
stituents, and the hydrogen at the tin atom interacting with the
aromatic ␲-system (3.092 Å) of a neighboring molecule (Fig. 1). In
the crystal structure of 6 (Fig. 2), the tin atom in this case is in a
tetrahedral environment. However, the tetrahedra is slightly dis-
torted, and a weak dative interaction between the nitrogen lone
pair and the central tin atom takes place (Fig. 2). The distance
between Sn and N (2.740(1) Å) is longer than the sum of the ionic
radii35 but still within the sum of the van der Waals radii.36 No
secondary interactions or supramolecular structure motifs are
observed for this substance. After exchange of one organic residue
In comparison to the 3-(halodiphenylstannyl)-N,N-dimethylpropan-
1-amine compounds published by the group of Jurkschat,16 all
Sn–N distances are approximately 0.22 Å shorter, and the Sn–X
distance 0.15 Å longer for our compounds, but the same trends
are displayed. However, compared to 3-(iododimethylstannyl)-
N,N-dimethylpropan-1-amine synthesized by Han, Sn–N (2.38(1) Å)
Published by NRC Research Press

568
Can. J. Chem. Vol. 92, 2014
Fig. 1. Molecular structure of triphenylstannane (16) and its secondary H-␲ interactions in solid state (30% ellipsoids).
Fig. 2. Molecular structure of triphenylaminopopyltin (6) and of 3-(diethyiodolstannyl)propan-1-amine (13) (30% ellipsoids).
Table 1. Crystallographic data and details of measurements for compounds 6, 11–16.
Compound
Ph3SnH (16)
Ph3SnA (6)
Et2SnAF (14)
Et2SnACl (11)
Et2SnABr (12)
Et2SnAI (13)
Et2SnAacetate (15)
Formula
C18H16Sn
351.00
10.2387(9)
17.0950(16)
8.6077(9)
90
C21H23NSn
408.09
7.9511(7)
7.7836(7)
14.6823(13)
90
C7H18FNSn
253.91
8.3288(3)
11.1680(4)
10.9091(4)
90
C7H18ClNSn
270.36
8.0696(3)
12.6624(5)
11.1410(4)
90
C7H18BrNSn
314.82
12.4587(6)
12.3707(6)
14.1833(6)
90
C7H18INSn
361.81
12.6749(4)
13.3911(4)
13.7536(4)
90
C9H21NO2Sn
293.96
7.7714(4)
13.4517(6)
11.9859(5)
90
Fw (g mol−1
a (Å)
)
b (Å)
c (Å)
␣ (°)
␤ (°)
99.248(5)
90
1487.0(2)
4
90.503(3)
90
908.63(14)
2
103.136(1)
90
988.17 (6)
4
103.395(2)
90
1107.42(7)
4
90
90
90
90
101.381(2)
90
1228.35(10)
4
␥ (°)
V (Å3)
2185.97(18)
8
2334.41(12)
8
Z
Crystal system
Space group
Monoclinic
P21/c
1.568
1.70
100(2)
Monoclinic
P21
1.492
Monoclinic
P21/n
1.707
Monoclinic
P21/n
1.622
2.49
100(2)
2.5–36.8
1947
101
536
0.069
Orthorhombic Orthorhombic Monoclinic
Pbca
1.913
5.94
Pbca
2.059
4.78
P21/n
1.590
2.06
d
calc (mg/m3)
␮ (mm−1
T (K)
)
1.41
2.54
100(2)
2.6–28.3
4189
219
412
100(2)
2.7–27.1
2169
101
504
100(2)
2.7–27.1
1921
100(2)
2.7–28.3
2907
101
100(2)
3.1–27.1
2702
2␪ range (°)
Independent reflns 2619
No. of params
F(000)
Rint
2.0–25.0
176
696
0.089
101
129
1216
0.024
1360
0.031
592
0.022
0.023
0.018
R1, wR2 (all data)
R1, wR2 (>2␴)
0.0536, 0.1327 0.0206, 0.0393 0.0174, 0.0370 0.0308, 0.1132 0.0223, 0.0506 0.0231, 0.0532
0.0475, 0.1236 0.0196, 0.0385 0.0148, 0.0353 0.0296, 0.1087 0.0212, 0.0500 0.0218, 0.0524
0.0245, 0.0434
0.0189, 0.0415
Note: Mo K␣ (␭ = 0.71073 Å). R1 = ⌺/|Fo| – |Fc|/|⌺|Fd; wR2 = [⌺w(Fo2 – F22)2/⌺w(Fo2)2]1/2
.
Published by NRC Research Press

Pichler et al.
569
Table 2. Selected bond lengths and angles.
Sn–C(Ph)
Sn–C(Et) Sn–C(amine) Sn–X
2.145(3)
Sn–N
N–H···X N–Sn–X
N–Sn–C(amine) X–Sn–C(amine)
Ph3SnH (16)
Ph3Sn[(CH2)3NH2] (6)
2.144(4)
2.151(3)
2.740(1)
175.81(11) 73.76(3)
2.194(3)trans to the amine
Et2Sn[(CH2)3NH2]F (14)
Et2Sn[(CH2)3NH2]Cl (11)
Et2Sn[(CH2)3NH2]Br (12)
Et2Sn[(CH2)3NH2]I (13)
Et2Sn[(CH2)3NH2]Acetate (15)
2.144(2) 2.153(2)
2.149(3) 2.146(2)
2.175(3) 2.151(3)
2.185(3) 2.152(3)
2.147(2) 2.150(2)
2.108(1) 2.387(1) 2.027(2) 170.59(11) 79.28(3)
91.38(2)
90.81(2)
92.47(2)
91.63(2)
95.67(2)
1.975(2)
2.623(1) 2.339(2) 2.414(1) 170.30(11) 79.49(3)
2.437(1)
2.796(4) 2.347(3) 2.776(1) 172.27(11) 79.89(3)
2.853(1)
3.060(3) 2.330(3) 2.940(1) 171.80(2) 80.43(3)
3.042(1)
2.027(1) 2.397(2) 2.160(1) 173.76(11) 78.88(3)
2.332(1)
Fig. 3. Supramolecular network formed by the fluoro (14) and chloro (11) (shown) derivatives as well as by the bromo (12) and iodo (13)
(shown) derivatives respectively (30% ellipsoids). Values shown in Å.
as well as Sn–I (3.0567(6) Å) bond lengths are of the same length as
in our compounds.37 Along with Han,37 we also observe a bond
length longer than the sum of the ionic radii,35 however this is
only observed for iodo compound 13. The other derivatives show
shorter bond lengths. The large difference compared to Jurkschat’s
compounds might be an electronic effect of the aromatic rings at
the tin atom. However, supramolecular structures were not men-
tioned.16 This suggests that the ability for the formation of hy-
drogen bonds is very important for the properties of this certain
type of molecule, at least in the solid state. With the fluo-
ro-derivative 14 in hand, we also performed solid state 119Sn and
119Sn{19F} CP MAS NMR experiments (Fig. 4) to eventually gain
some insight into the bonding nature between the tin and the
halogen atom in our compounds. With a 1J(119Sn-19F) coupling con-
stant of 1920 Hz, no tremendous change is observed compared to
the coupling constant of 2069 Hz in a CDCl3 solution.
This suggests that at least the fluoro compound 14 is not present
as an ionic compound, neither in the solid state nor in an apolar
solution. Larger differences are observed for the chemical shifts
than for the coupling constants. For 119Sn with –34.8 ppm (solu-
tion) versus 74.2 ppm (s-st), a downfield shift is observed in the
solid state. In the case of 19F, an even larger downfield shift from
–175.0 ppm in solution to 21.2 ppm in the solid state occurs. The
large difference for the fluorine shifts, in particular, might be
caused by the formation of the hydrogen bond network in the
solid state, as shown by X-ray structure analysis (Fig. 3), an effect
which should not be present in solution. Solution 119Sn NMR data
of the different halogenides (11–14) shows an unusual, narrow
shift range of ϳ10 ppm starting at –25.5 ppm and ending at
–34.8 ppm [Cl(–25.5) ϳ Br(–25.9) > I(–30.7) > F(–34.8)]. In compara-
ble compounds without donor atoms, a larger difference in the
chemical shift is observed as well as a strong low-field shift. As an
example, NMR data for the n-Bu3SnX is given (X=Cl, Br, I) as fol-
lows: [Cl(152.0) > Br(138.5) > I(89.9)].38 For X=F no solution NMR
data is available due to insolubility. Additional NMR experiments
on our compounds are currently ongoing. Defined amounts of
donor molecules (e.g., THF, pyridine, HMPA) are added to the NMR
solutions of 11, and the changes in the NMR shifts as well as in the
coupling constants are investigated and also VT-NMR studies con-
ducted. The results will be published elsewhere.
Conclusion
We were able to introduce a new versatile route to aminopropyl
tin compounds in very good yields. We also first synthesized ami-
nopropyl tin halides with acidic hydrogens present at the ni-
trogen atom via a so far unknown thermally induced proto
dearylation reaction of aminopropyl tin hydrohalides. It was also
possible to transform these compounds into the fluoride and ac-
etate. For all of these substances a full set of NMR data and in the
case of solid products also X-ray structures were obtained showing
interesting structural properties differing form the so far litera-
ture known N,N-dimethylaminopropyl tin derivatives.
Experimental
Materials and methods
All moisture and air sensitive reactions were carried out under
inert atmosphere using Schlenk techniques unless otherwise
Published by NRC Research Press

570
Can. J. Chem. Vol. 92, 2014
Fig. 4. Solid-state 119Sn MAS NMR spectrum of compound 14, which
was recorded at a spinning speed of 30 kHz with the bearing gas at
ambient temperature. Asterisks indicate spinning side bands. The
magnification in the upper right corner includes the 119Sn {19F} CP
MAS experiment (red), which proves that the coupling constant
J [kHz] = 1.8 of the doublet in the Hahn-echo experiment [␶ = 4
(131 ␮s @ 30 kHz)] (black) is a result of the 119Sn - 19F coupling. Please
see the online version for colour.
NMR Spectroscopy
Solution 1H (300.22 MHz), 13C (75.50 MHz), and 119Sn (111.92 MHz)
NMR spectra were recorded on a Mercury 300 MHz spectrometer
from Varian at 25 °C. Chemical shifts are given in parts per million
(ppm) relative to TMS (␦ = 0 ppm) regarding 13C and 1H, and rela-
tive to SnMe4 in the case of 119Sn. Coupling constants (J) are re-
ported in Hertz (Hz). All NMR measurements were taken in CDCl3,
with exception of tin hydrides that were measured in C6D6 to
avoid chlorination of the tin atom. For complete peak assignment,
multinuclear NMR experiments were also carried out (H,H-COSY
and C,H-HETCOR). Solid state high-resolution, i.e., magic angle
spinning (MAS), 19F and 119Sn-NMR spectra were acquired using an
Avance III NMR spectrometer (Bruker BioSpin) connected to a
cryomagnet with a nominal field of 11.7 T. This resulted in reso-
nance frequencies of 186.5 MHz for 119Sn and 470.4 MHz for 19F,
respectively. A standard (double-resonance) 2.5 mm probe (Bruker),
which can be operated at spinning speeds of up to 30 kHz, was
used for the experiments. 119Sn MAS NMR spectra were referenced
to solid SnO2, which shows its resonance signal at –604.3 ppm
relative to the primary reference SnMe4 (0 ppm). The spectra were
recorded using a rotor-synchronized Hahn-echo pulse sequence
(␲/2-␶-␲-␶-acquire; ␶ denotes the rotor period) and a standard cross-
polarization (CP) pulse sequence, respectively. 119Sn{19F} CP MAS
NMR was used with a flip-back pulse on the 19F spins following
data acquisition. Recycling delays of 600 s for the Hahn-echo ex-
periment and 360 s for the CP experiment were used. The sample
under investigation was used to set the Hartman–Hahn match
under MAS conditions with the match optimized for a 30 kHz
spinning speed. Processing of the data was carried out using Top-
Spin 3.1 software (Bruker) and MestReNova7 (Mestrelab research).
Crystal structure determination
All crystals suitable for single crystal X-ray diffractometry were
removed from a Schlenk flask under a stream of N2 and immedi-
ately covered with a layer of silicone oil. A single crystal was
selected, mounted on a glass rod on a copper pin, and placed in
the cold N2 stream provided by an Oxford Cryosystems cryometer.
XRD data collection was performed on a Bruker Apex II diffrac-
tometer with use of Mo K␣ radiation (␭ = 0.71073 Å) and a CCD area
detector. Empirical absorption corrections were applied using
SADABS.40 The structures were solved with use of either direct
methods or the Patterson option in SHELXS and refined by the
full-matrix least-squares procedures in SHELXL.41,42 Non-hydrogen
atoms were refined anisotropically. Hydrogen atoms bonded to N1
for all compounds were located in a difference map and in some
instances refined with distance restraints (SADI). Other hydrogen
atoms were located in calculated positions corresponding to stan-
dard bond lengths and angles. In compound 16, the hydrogen
atom next to the heavy atom Sn was found on the difference
Fourier map, however it should be noted that a common problem
exists with locating light atoms (hydrogen) next to heavy atoms
because of their poor scattering abilities. Multiple attempts to
model disorder for the ethyl substituents in compound 12 re-
sulted in unstable refinements. However the residual electron
density was well below acceptable values. Compound 6 was
twinned and was refined using the TWIN option in SHELXL, and
the matrix (1 0 0 0 –1 0 0 0 –1 4) was applied. The contributions of
the three twin components refined to 0.300(2)/0.857(2)/0.552(2).
stated. Nitrogen was used as inert gas and passed through molec-
ular sieve of 4 Å and P5O10 with moisture indicator (Sicapent by
Merck) to remove trace water. Solvents were stored over a drying
®
agent (LAH in case of THF, P5O10 for CH2Cl2, and (MeO)2Mg for
methanol) under N2 and distilled prior to use or taken directly
from an Innovative Technology solvent drying system (benzene,
®
heptane). CDCl3 was distilled over P5O10 and stored under N2. C6D6
was distilled over sodium and stored over a potassium mirror
under N2. All chemicals were used as received from various chem-
ical suppliers without any further purification. Tin monohydrides
(16–18) were synthesized from the corresponding tin chlorides
according to the preparation method of Finholt,25,26 using lith-
ium aluminum hydride (LAH) in Et2O. These tin chlorides were
easily accessible with different aromatic and aliphatic substitu-
ents via various literature procedures. Kocheskov redistribu-
tion,39 as well as hydro dearylation with HCl, and subsequent
treatment with organometallic reagents (e.g., Grignard or organo-
lithium reagents) yields the desired substitution patterns in the
starting materials. However the synthesis of these substances is
not stated in this paper and only spectroscopic data for the tin
hydrides is provided. TGA/DSC/MS measurements were conducted
on a TG-DSC STA 409 TASC 414/3C/3/F connected to a QMS 403 C by
a capillary coupling (both by NETZSCH). Samples were measured
in an Al crucible on a Pt sample carrier RG-2 in a temperature
range of 35 °C to 540 °C with a ramp of 10 K/min under a He flow
of 200 mL/min as inert gas. The following m/z values were tracked
during the experiment: 2, 12, 14, 15, 16, 17, 18, 26, 30, 35, 38, 41, 44,
51, 59, 77, 78, 119. All elemental analyses were performed on a
Heraeus VARIO ELEMENTAR EL analyzer. Melting points were de-
termined with a STUART SCIENTIFIC SMP 10, no temperature cor-
rections were applied.
(E)-N-(3-chloropropyl)-2,2-dimethylpropan-1-imine 1
In a 500 mL round-bottomed flask attached to a Dean–Stark trap
and a N2 supply, 3-chloropropan-1-amine hydrochloride (13 g,
0.10 mol/L, 1.0 equiv.), 2,2-dimethylpropanal (8.6 g, 0.10 mol/L,
1.0 equiv.), and KOH (5.6 g, 0.10 mol/L, 1.0 equiv.) were suspended
in 250 mL of benzene. The suspension was heated under reflux
until no more H2O was generated. The solvent was distilled off
under atmospheric pressure. Fractionation over a 20 cm Vigreux-
collum under reduced pressure afforded (E)-N-(3-chloropropyl)-2,2-
Published by NRC Research Press

Pichler et al.
571
dimethylpropan-1-imine (1) as colorless liquid (9.4 g, 58%). B.p.:
60 °C at 12 mbar (1 bar = 100 kPa). The product is stored under N2
at –18 °C. 1H-NMR ␦: 7.48 (t, 1H, 4J = 2.5, N = CH); 3.44 (t, 2H, 3J = 12.9,
CH2CH2Cl); 3.41 (td; 2H, 3J = 14.1, CH2N); 1.96 (p, 2H, CH2CH2CH2);
0.98 (s, 9H, CH3). 13C-NMR ␦: 173.3 (N = CH); 57.6 (N-CH2); 42.6
(Cl-CH2); 36.3 (C quart.); 33.2 (CH2CH2CH2); 27.0 (3C, CH3). Elemen-
tal analysis (calcd.): C: 58.2% (59.4%); H: 9.6% (10.0%); N: 8.9% (8.7%).
filtered, and the solution evaporated again. The resulting color-
less to slightly orange-red amines are dried in oil-vacuum at 50 °C
for 2 h. They are usually pure according to 1H-NMR but might be
distilled under vacuum if necessary.
3-(Triphenylstannyl)propan-1-amine hydrochloride 5
Amorphous white solid. Yield: 95.4%. M.p.: 162–163 °C (dec.).
1H-NMR ␦: 8.60–7.85 (s, 3H, CH2N+H3); 7.65–7.43 (m, 5H, o-Ph);
7.42–7.25 (m, 10H, m,p-Ph); 2.86 (t, 2H, CH2N); 2.10 (p, 2H,
CH2CH2CH2); 1.46 (t, 2H, CH2Sn) 13C-NMR ␦: 137.7 (3C, 1J(119Sn-13C) =
General procedure for alkylation of tin hydrides
A Schlenk tube is charged with LDA (2.3 g, 1.05 equiv.) dissolved
in 50 mL THF. The desired tin hydride (20 mmol/L, 1.0 equiv.) was
added dropwise at 0 °C under vigorous stirring. The slightly or-
ange to red solution was stirred for another 5 min. In a second
Schlenk tube electrophile (1) (3.2 g, 1.0 equiv.) was diluted in 25 mL
THF and cooled to 0 °C. The freshly prepared stannide solution is
then cannulaed dropwise on the electrophile solution under vig-
orous stirring. The cooling bath is removed and the solution is
allowed to stir for an additional 10 min at RT. The solvent is then
removed under reduced pressure, the residue suspended in 20 mL
CH2Cl2 and stirred for 10 min at RT. The mixture is filtered
through Celite , washed 2 times with 10 mL CH2Cl2 and then the
1
2
2
503, J(117Sn-13C) = 480, i-Ph); 136.9 (6C, J(119Sn-13C) = 37, J(117Sn-
13C) = 35, o-Ph); 129.0 (3C, 4J(119/117Sn-13C) = 11, p-Ph); 128.6 (6C,
3J(119Sn-13C) = 50, J(117Sn-13C) = 48 , m-Ph); 42.9 (3J(119Sn-13C) = 85,
3
3J(117Sn-13C) = 79, N-CH2); 24.8 (2J(119/117Sn-13C) = 16, CH2CH2CH2); 7.0
(1J(119Sn-13C) = 374, J(117Sn-13C) = 357, CH2Sn) 119Sn-NMR ␦: –102.8.
1
Elemental analysis (calcd.): C: 56.3% (56.7%); H: 5.5% (5.4%); N: 3.2%
(3.2%).
3-(Triphenylstannyl)propan-1-amine 6
Colorless crystals out of ethyl acetate. Yield: 96.3%. M.p.: 71–
73 °C. 1H-NMR ␦: 7.60–7.51 (m, 6H, o-Ph); 7.41–7.34 (m, 9H, m,p-Ph);
2.73 (t, 2H, CH2NH2); 1.86 (p, 2H, CH2CH2CH2); 1.50 (t, 2H, CH2Sn);
1.28 (s, 2H, CH2NH2). 13C-NMR ␦: 139.3 (3C, 1J(119Sn-13C) = 489,
1J(117Sn-13C) = 467 Hz, i-Ph); 136.7 (6C, 2J(119Sn-13C) = 36, 2J(117Sn-13C) =
®
solvent pumped down again. The product is dried under oil vac-
uum at 50 °C for 2 h. The resulting colorless to slightly orange-red
imines are oily liquids and usually pure according to 1H-NMR but
might be distilled under oil-vacuum if necessary.
3
35, o-Ph); 128.7 (3C, 4J(119/117Sn-13C) = 11, p-Ph); 128.4 (6C, J(119Sn-
3
3
13C) = 49, J(117Sn-13C) = 47, m-Ph); 45.7 (3J(119Sn-13C) = 68, J(117Sn-
13C) = 65, N-CH2); 30.4 (2J(119/117Sn-13C) = 22, CH2CH2CH2); 7.9
(1J(119Sn-13C) = 402, 1J(117Sn-13C) = 374), CH2Sn). 119Sn-NMR ␦: –102.7.
Elemental analysis (calcd.): C: 61.6% (61.8%); H: 5.8% (5.7%); N: 3.5%
(3.4%).
(E)-2,2-dimethyl-N-(3-(triphenylstannyl)propyl)propan-1-imine 2
Slightly yellow oil. Yield: 94.3%. 1H-NMR ␦: 7.50–7.41 (m, 6H, o-Ph);
7.30 (s, 1H, N=CH); 7.29–7.23 (m, 9H, m,p-Ph); 3.29 (t, 2H, CH2N); 1.91
(p, 2H, CH2CH2CH2); 1.37 (t, 2H, CH2Sn); 0.95 (s, 9H, CH3). 13C-NMR
␦: 172.3 (N=CH); 138.8 (3C, 1J(119Sn-13C) = 487, 1J(117Sn-13C) = 465, i-Ph);
137.0 (6C, 2J(119Sn-13C) = 36, 2J(117Sn-13C) = 35, o-Ph); 128.8 (3C,
4J(119/117Sn-13C) = 11, p-Ph); 128.4 (6C, 3J(119Sn-13C) = 49, 3J(117Sn-13C) =
47, m-Ph); 64.7 (3J(119Sn-13C) = 68, 3J(117Sn-13C) = 65, N-CH2); 35.9
(C-quart.); 27.7 (2J(119/117Sn-13C) = 19, CH2CH2CH2); 27.0 (3C, CH3); 8.1
3-(Diphenyl(propyl)stannyl)propan-1-amine hydrochloride 7
Amorphous white solid. Yield: 96.1%. M.p.: 114–116 °C (dec.). 1H-
NMR ␦: 8.28 (s, 3H, NH3); 7.53–7.27 (m, 10H, aromatic); 2.67 (s, 2H,
CH2N); 2.08–1.90 (m, 2H, CH2CH2CH2NH3); 1.75–1.60 (m, 2H, aliphatic);
1.37–1.29 (m, 2H, aliphatic); 1.27–1.19 (m, 2H, CH2CH2CH2NH3);
0.98 (t, 3H, methyl). 13C-NMR ␦: 139.0 (2C, i-Ph); 136.7 (4C, o-Ph);
128.7 (2C, p-Ph); 128.4 (4C, m-Ph); 43.1 (N-CH2); 24.9 CH2CH2CH2N);
20.2 (CH2CH2CH3); 18.9 (CH2CH2CH3); 13.0 (CH2CH2CH3); 6.5
CH2CH2CH2N). 119Sn-NMR ␦: –72.9. Elemental analysis (calcd.): C:
52.8% (52.7%); H: 6.4% (6.4%); N: 3,4% (3.4%).
1
(1J(119Sn-13C) = 395, J(117Sn-13C) = 377), CH2Sn). 119Sn-NMR ␦: –99.5.
Elemental analysis (calcd.): C: 65.5% (65.6%); H: 6.5% (6.6%); N: 3.0%
(2.9%).
(E)-N-(3-(diphenyl(propyl)stannyl)propyl)-2,2-dimethylpropan-1-
imine 3
Slightly orange oil. Yield: 91.3% 1H-NMR ␦: 7.63–7.54 (m, 4H, o-Ph);
7.51 (s, 1H, N=CH); 7.46–7.31 (m, 6H, m,p-Ph); 3.46 (t, 2H, CH2N);
2.08–1.90 (m, 2H, CH2CH2CH2N); 1.86–1.64 (m, 2H, CH2CH2CH3);
1.45–1.20 (m, 4H, aliphatic); 1.14 (s, 9H, methyl); 1.09 (t, 3H, meth-
yl). 13C-NMR ␦: 171.9 (N=CH); 140.0 (2C, i-Ph); 136.7 (4C, o-Ph);
128.3 (2C, p-Ph); 128.1 (4C, m-Ph); 64.8 (N-CH2); 35.8 (C-quart.); 27.7
(CH2CH2CH2N); 26.9 (3C, CH3); 20.1 (CH2CH2CH3); 18.8
(CH2CH2CH3); 13.0 (CH2CH2CH3); 7.4 (CH2CH2CH2N). 119Sn-NMR ␦:
–73.1.
3-(Diphenyl(propyl)stannyl)propan01-amine 8
1
Slightly yellow oil. Yield: 95.8%. H-NMR ␦: 7.54–7.30 (m, 10H,
aromatic); 2.69 (t, 2H, CH2NH2); 1.81–1.63 (m, 4H, aliphatic); 1.35–
1.11 (m, 6H, aliphatic, NH2); 1.00 (t, 3H, SnCH2CH2CH3). 13C-NMR ␦:
140.3 (2C, i-Ph); 136.7 (4C, o-Ph); 128.4 (2C, p-Ph); 128.2 (4C, m-Ph);
46.0 (N-CH2); 30.7 (CH2CH2CH2NH2); 20.2 (CH2CH2CH3); 18.9
(CH2CH2CH3); 13.2 (CH2CH2CH3); 7.3 (CH2CH2CH2NH2). 119Sn-NMR
␦: –72.9. Elemental analysis (calcd.): C: 57.3% (57.8%); H: 6.6% (6.7%);
N: 3.8% (3.7%).
(E)-N-(3-(diethyl(phenyl)stannyl)propyl)-2,2-dimethylpropan-1-
imine 4
3-(Diethyl(phenyl)stannyl)propan-1-amine hydrochloride 9
Colorless oil. Yield: 92.5% 1H-NMR ␦: 7.40–7.33 (m, 3H, o-Ph,
N=CH); 7.28–7.16 (m, 3H, m,p-Ph); 3.26 (t, 2H, CH2N); 1.82–1.65 (m,
2H, CH2CH2CH2N); 1.32–0.75 (m, 21H, aliphatic). 13C-NMR ␦: 172.0
(N=CH); 141.1 (i-Ph); 136.5 (2C, o-Ph); 128.0 (p-Ph); 128.0 (2C, m-Ph);
65.1 (N-CH2); 35.9 (C-quart.); 27.9 (CH2CH2CH2N); 27.0 (3C, CH3);
10.9 (2C, CH2CH3); 5.9 (CH2CH2CH2N); 1.1 (2C, CH2CH3). 119Sn-NMR
␦: –34.3.
Colorless oil. Yield: 99.8%. 1H-NMR ␦: 8.08 (s, 3H, NH3); 7.37–7.28 (m,
2H, o-Ph); 7.27–7.11 (m, 3H, m,p-Ph); 2.80 (t, 2H, CH2CH2CH2NH3);
1.93–1.77 (m, 2H, CH2CH2CH2NH3); 1.30–0.80 (m, 12H, aliphatic).
13C-NMR ␦: 140.0 (i-Ph); 136.5 (2C, o-Ph); 128.4 (p-Ph); 128.2 (2C,
m-Ph); 43.3 (N-CH2); 25.0 (CH2CH2CH2N); 10.9 (2C, methyl); 5.0
(CH2CH2CH2N); 1.2 (2C, CH2CH3). 119Sn-NMR ␦: –35.0. Elemental
analysis (calcd.): C: 44.5% (44.8%); H: 6.7% (6.9%); N: 3.9% (4.0%).
General procedure for hydrolysis of aminopropyl tin imines
A 250 mL round-bottomed flask is charged with the desired
imine (10 mmol/L, 1.0 equiv.) and 50 mL THF. 1.0 equiv. of 0.1 N
aqueous HX (X=Cl, Br, I) is added under stirring. The resulting
milky suspension is completely evaporated on the rotavap at 50 °C.
The resulting colorless to slightly orange amino-hydrochlorides
are dissolved in 50 mL MeOH containing 1.0 equiv. KOH. MeOH is
removed on the rotavap, the residue suspended in 20 mL CH2Cl2,
3-(Diethyl(phenyl)stannyl)propan-1-amine 10
Slightly yellow oil. Yield: 96.8%. H-NMR ␦: 7.53–7.40 (m, 2H,
1
o-Ph); 7.40–7.24 (m, 3H, m,p-Ph); 2.66 (t, 2H, CH2CH2CH2NH2); 1.83–
1.59 (m, 2H, CH2CH2CH2NH2); 1.34–0.88 (m, 14H, aliphatic, NH2).
13C-NMR ␦: 141.1 (i-Ph); 136.4 (2C, o-Ph); 128.0 (p-Ph); 127.9 (2C, m-
Ph); 46.0 (N-CH2); 30.8 (CH2CH2CH2N); 10.9 (2C, methyl); 5.6
(CH2CH2CH2N); 1.1 (2C, CH2CH3). 119Sn-NMR ␦: –34.7.
Published by NRC Research Press

572
Can. J. Chem. Vol. 92, 2014
General procedure for aminopropyl tinhalogenides
1H-NMR ␦: 2.73 (t, 2H, CH2NH2); 1.95 (s, 3H, C=OCH3); 1.88 (s, 2H,
CH2NH2); 1.78 (p, 2H, CH2CH2CH2); 1.36–0.95 (m, 12H, CH2CH2CH2Sn,
CH3CH2Sn, CH3CH2Sn). 13C-NMR ␦: 176.8 (C=O); 42.7 (3J(119/117Sn-
13C) = 34, N-CH2); 26.9 (2J(119/117Sn-13C) = 29, CH2CH2CH2); 23.0
(O=CCH3); 10.6 (2C, 2J(119/117Sn-13C) = 40, CH3); 10.3 (2J(119/117Sn-13C) =
495, CH2CH2Sn); 9.7 (2C, CH3CH2Sn, 2J(119/117Sn-13C) = 506). 119Sn-
NMR ␦: –53.0. Elemental analysis (calcd.): C: 36.8% (36.8%); H: 7.2%
(7.2%); N: 4.8% (4.8%).
10 mmol/L of the desired aminopropyltin hydrohalide (chloride,
bromide, iodide) is placed in a Schlenk tube equipped with a
reflux condenser and a vacuum supply on the top of the reflux
condenser. Vacuum is applied to the apparatus and the tube
placed in an oil bath under siring. The oil bath is then heated until
evolution of benzene is visible and held at this temperature. After
gas evolution has stopped, the flask is heated up until the product
starts to distill into the reflux condenser (usually around 200 °C).
The whole apparatus is then allowed to cool down to RT. After-
wards the product is washed into a second flask with CH2Cl2. The
solvent is then removed in vacuum and the product recrystallized.
Triphenylstannane 16
Colorless crystals out of pentane. M.p.: 27–28 °C. Yield: 91.2%.
1H-NMR ␦: 7.54–7.48 (m, 6H, o-Ph), 7.15–7.11 (m, 9H, m,p-Ph), 6.91 (s,
1
1
1H, J(1H-119Sn) = 1934, J(1H-117Sn) = 1848, Sn-H). 13C-NMR ␦: 137.7
(6C, 2J(13C-119Sn) = 41, 2J(13C-117Sn) = 39, o-Ph), 137.3 (3C, 1J(13C-119Sn) =
3-(Chlorodiethylstannyl)propan-1-amine 11
534, J(13C-117Sn) = 511, i-Ph), 129.3 (3C, 4J(13C-119/117Sn) = 11, p-Ph),
1
Colorless crystals out of benzene. Yield: 92.1%. M.p.: 140–141 °C.
1H-NMR ␦: 2.64 (s, 2H, CH2NH2); 1.70 (p, 2H, CH2CH2CH2); 1.60 (s,
2H, CH2NH2); 1.27–0.93 (m, 12H, CH2CH2CH2Sn, CH3CH2Sn,
129.0 (6C, J(13C-119Sn) = 53, J(13C-117Sn) = 50, m-Ph). 119Sn-NMR ␦:
3
3
–162.8. Elemental analysis (calcd.): C: 61.4% (61.6%); H: 4.5% (4.6%).
3
CH3CH2Sn). 13C-NMR ␦: 42.9 (3J(119Sn-13C) = 37, J(117Sn-13C) = 35,
N-CH2); 29.7 (2J(119/117Sn-13C) = 30, CH2CH2CH2); 13.3 (1J(119Sn-13C) =
490, 1J(117Sn-13C) = 468, CH2CH2Sn); 12.0 (2C, 1J(119Sn-13C) = 495,
Diphenyl(propyl)stannane 17
1H-NMR ␦: 7.51–7.41 (m, 4H, o-Ph); 7.21–7.06 (m, 6H, m,p-Ph);
6.28 (s, 1H, 1J(119Sn-1H) = 1804, 1J(117Sn-1H) = 1723, Sn-H); 1.65–1.49 (m,
2H, SnCH2CH2CH3); 1.19 (t, 2H, SnCH2CH2CH3); 0.88 (t, 3H,
SnCH2CH2CH3). 13C-NMR ␦: 138.3 (4C, o-Ph); 137.5 (2C, i-Ph);
129.0 (2C, p-Ph); 128.8 (4C, m-Ph); 20.9 (SnCH2CH2CH3); 18.8
(SnCH2CH2CH3); 13.1 (SnCH2CH2CH3). 119Sn-NMR ␦: –139.8.
2
2
1J(117Sn-13C) = 473, CH3CH2Sn); 10.7 (2C, J(119Sn-13C) = 33, J(117Sn-
13C) = 32), CH3). 119Sn-NMR ␦: –25.5. Elemental analysis (calcd.): C:
31.0% (31.1%); H: 6.6% (6.7%); N: 5.2% (5.2%).
3-(Bromodiethylstannyl)propan-1-amine 12
Colorless crystals out of benzene. Yield: 94.3%. M.p.: 99–100 °C.
1H-NMR ␦: 2.70 (s, 2H, CH2NH2); 2.00–1.50 (m, 4H, CH2CH2CH2,
CH2NH2); 1.50–1.00 (m, 12H, CH2CH2CH2Sn, CH3CH2Sn, CH3CH2Sn).
13C-NMR ␦: 43.0 (3J(119/117Sn-13C) = 38, N-CH2); 26.9 (2J(119/117Sn-13C) =
30, CH2CH2CH2); 14.7 (1J(119Sn-13C) = 471, 1J(117Sn-13C) = 451, CH2CH2Sn);
12.7 (2C, 1J(119Sn-13C) = 475, 1J(117Sn-13C) = 455, CH3CH2Sn); 10.9 (2C,
2J(119/117Sn-13C) = 33), CH3). 119Sn-NMR ␦: –25.9. Elemental analysis
(calcd.): C: 26.1% (26.7%); H: 5.5% (5.8%); N: 4.5% (4.5%).
Diethyl(phenyl)stannane 18
1H-NMR ␦: 7.48–7.38 (m, 2H); 7.20–7.01 (m, 3H); 6.05 (s, 1H,
1J(119Sn-1H) = 1813, 1J(117Sn-1H) = 1734); 1.34–0.88 (m, 10H). 13C-NMR ␦:
138.9 (i-Ph); 137.4 (2C, o-Ph); 128.7 (p-Ph); 128.6 (2C, m-Ph); 11.8 (2C,
methyl); 1.1 (2C, SnCH2CH3). 119Sn-NMR ␦: –98.5.
Supplementary data
Supplementary data are available with the article through the
journal Web site at http://nrcresearchpress.com/doi/suppl/10.1139/
cjc-2013-0504. CCDC Nos. 969138–969144 contain the supplemen-
tary crystallographic data for compounds 6 and 11–16, respectively.
These data can be obtained, free of charge, via http://www.ccdc.
cam.ac.uk/products/csd/request (Or from the Cambridge Crystallo-
graphic Data Centre, 12 Union Road, Cambridge CB2 1E2, UK;
fax: +44 1223 33603; or e-mail: deposit@ccdc.cam.ac.uk).
3-(Diethyiodolstannyl)propan-1-amine 13
Colorless crystals out of benzene. Yield: 95.1%. M.p.: 113–114 °C.
1H-NMR ␦: 2.84 (t, 2H, CH2NH2); 2.06 (s, 2H, CH2NH2); 1.83 (p, 2H,
CH2CH2CH2); 1.47 (t, 2H, CH2CH2CH2Sn); 1.42–1.25 (m, 10H,
CH3CH2Sn, CH3CH2Sn). 13C-NMR ␦: 43.2 (3J(119/117Sn-13C) = 37,
N-CH2); 27.2 (2J(119/117Sn-13C) = 32, CH2CH2CH2); 16.6 (CH2CH2Sn);
13.7 (2C, CH3CH2Sn); 11.4 (2C, 2J(119/117Sn-13C) = 33; CH3). 119Sn-NMR
␦: –30.7. Elemental analysis (calcd.): C: 23.0% (23.2%); H: 5.0% (5.0%);
N: 3.9% (3.9%).
Acknowledgements
We thank Dr. Otto Fruhwirth for conducting the DGA/DSC-MS
measurements. This work was supported by the NAWI Graz proj-
ect, a collaboration between the Graz University of Technology
and the Graz University and the COST Action 1302 Smart Inor-
ganic Polymers.
3-(Diethylfluorostannyl)propan-1-amine 14
In a Schlenk tube 1.5 g (5.5 mmol/L, 1.0 equiv.) 3-(chlorodiethylstannyl)
propan-1-amine (5) are dissolved in 20 mL acetone/THF 1:1 and 0.32 g
(1.0 equiv.) potassium fluoride are added under stirring at RT. After
2 h the solvent is removed in vacuum. The residue is suspended in
CH2Cl2, filtered and the solvent removed again. The product is
recrystallized out of benzene to yield 3-(diethylfluorostannyl)propan-
1-amine as colorless, clear crystals (0.72 g, 51.2%). M.p.: 125–126 °C.
1H-NMR ␦: 2.60 (t, 2H, CH2NH2); 1.70 (p, 2H, CH2CH2CH2); 1.55
(s, 2H, CH2NH2); 1.19 (t, 6H, CH3CH2Sn); 1.09–0.95 (m, 6H,
CH2CH2CH2Sn, CH3CH2Sn). 13C-NMR ␦: 42.5 (3J(119/117Sn-13C) =
36 Hz, N-CH2); 26.8 (2J(119/117Sn-13C) = 28 Hz, CH2CH2CH2); 10.4 (2C,
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