EXPERIMENTS IN ORGANOTIN CHEMISTRY

Abstract
In this paperwork, two organotin products were produced. The first one was
dimethyldiphenyltin and the second one was dibenzyldiphenyltin. However the other
team will be doing other organotin products that are propyl and allyl.The purpose of
this paperwork is to compare and contrast different behavior of these organotin
products towards chemical reaction. The discussion will be about satellite
phenomenon that occur in
1
H NMR. The results will be discussed later in this
paperwork.

Introduction
Tin(Sn) is located in Group 14 in the periodic table. Organic compounds that consists
of Sn are not as popular as the others but still can bring many benefits to us. The first
organotin compound was discovered by Edward Frankland in 1849 that was called
diethyltin diiodide. Sn come from group 14 in the periodic table hence it tin have four
valence electrons.It have +2 and +4 oxidation states(4).The reaction of tin have been
conducted for the most of times as it is very highly economic and can make our life
better.Tin is used in many areas but the main are heat stabilizers,catalytic agents
and biocidal compunds(3).Thermal degradation of many chlorinated compunds for
instance transformer oils,PVC and modified plastics can be stabilize by organotin
which will act as stabilizers.They are used as cataslysts as well especially in
urethane formation and very helpful in agriculture and wood preservatives in biocidal
activity.(4)
COSHH form

Experimental
Outline of the experiment

1) To prepare the Grignard reagent
MeI + Mg MeMgI

2) To prepare organotin compound
Ph
2
SnCl
2
+ 2MeMgI Ph
2
SnMe
2


Preparation of Grignard reagent MeI + Mg MeMgI

The reaction flask was dried thoroughly by using an oven. The apparatus was set up
as shown below


Figure 1.Set up apparatus to produce Grignard reagent copied from reference (5)

The nitrogen gas was used to flush out the apparatus whilst the pressure equalizing
funnel was charged with a homogeneous solution of iodomethane (3.0g,21mmol,1.5
cm
3
) in dry diethyl ether (10 cm
3
). Magnesium turnings (0.50g,20mmol) were quickly
added through a wide-stem funnel and was covered with dry diethyl ether (10 cm
3
) .A
crystal of iodine was dropped carefully into the reaction flask. Stirring was not started
yet. 5 cm
3
of solution was added from the pressure equalizing funnel and the reaction
was started. The flask became warm when the bubbles appeared. The flask was
warmed to help the reaction by using a bowl of warm water. When the brown colour
of iodine decolourise , stirring was started. The iodomethane solution was added with
gentle refluxing.





Preparation of organotin compound ,Ph
2
SnCl
2
+ 2MeMgI Ph
2
SnMe
2


At this time, nitrogen protection was no longer needed.

Dichlorodiphenyltin (2.5g,7.3mmol) was dissolved in dry diethyl ether (25 cm
3
)
and was added into the pressure equalizing funnel. The source heat was removed
from the flask and the stirring was maintained. The solution of tin compound was
added to the Grignard reagent in rate of droplets continuous stream. The addition
was completed approximately about 20 minutes. Stirring was continued futher for half
hour and was refluxed by using water bath at 60
o
C

Hydrolysis of excess Grignard reagent.
Aqueous ammonium chloride solution (10g/50 cm
3
) was added and two layers will be
formed. The mixture was stirred vigorously at this stage.

Isolation of organotin compound

The reaction flask was poured into a 250 cm
3
separating funnel and two layers were
observed. Note : The lower layer was the ammonium chloride solution. The ether
layer was collected and the aqueous layer was extracted by using diethyl ether ( 2 x
50 cm
3
). The combined ether layer was then extracted and was dried over
magnesium sulphate. Then,the dried ether layer was evaporated by using rotary
evaporator. Colourless oil of organotin compound was produced.

Purification of the organotin compound

The crude organotin compound (2 cm
3
) was transferred to a 25 cm
3
round bottomed
flask and was distilled under reduced pressure by using a Kugelrohr apparatus and a
trolley pump.
Note: Dimetyldiphenyltin distills at approximately 116
0
C / 0.3 mmHg.

Results and analysis
Yield 1.08g ,48%,

Boiling point 116
0
C at 0.3 mmHg.



Figure2. Infrared spectrum of dimethyldiphenyltin

Analysis of the IR spectrum

Observed peaks (cm
-1
) Assignments Quoted range(cm
-1
)
3062.69-2988.05 C-H stretching vibrations
in aromatic compounds
3080-3030

1480.40 and 1427.42 C=C stretching vibrations
in aromatic compound
1465-1440

3136.07-2915.55 C-H stretching vibrations 3000-2850


Figure3.
1
H NMR of the dimethyldiphenyltin

Analysis of the
1
H NMR

Chemical
shift(ppm)

Multiplicity

J(Hz)

Integration

Assignments

0.5024

s - 7.8 (6H) H
a
7.423

s - 13.1 (10H) H
b










Discussion
By principle,the peak at 7.423 (aromatic ring) should be singlet because Sn do not
have any proton that will be coupled to the proton in the phenyl ring. But as we can
see,there seems small peaks shouldering the main
1
H NMR. These peaks are not
because of the proton-proton coupling. These small peaks are known as satellite to
the main peak. This is due to the coupling of the
1
H atoms to the isotopes of the Sn.
The coupling is also due to the proton coupled to an I=0.5 that is not 100% naturally
abundant. Hence,the splitting due to a single spin=0.5 coupled to the Sn isotope
should be doublet. The proton coupled to the more abundant Sn is not split so an
intense singlet was produced as shown in the Figure 3. To conclude, we get the
result as a pair of evenly spaced small signals that seems around the main peak.
Sn has ten stable isotopes in natural abundance and three out of ten have I=0.5 and
the remaining I=0. The peak at 1.18 ppm is due to the solvent that we used that is
diethyl ether.
These are Sn isoptopes that have I=0.5
119
Sn 8.6%,
117
Sn 7.7%,
115
Sn 0.4%
Diphenyldimethyltin has
2
J
SnH
54.2Hz ,42.3 Hz ,37.5 Hz for
119
Sn,
117
Sn and
115
Sn.



















However,we cannot proceed to the next part for the reaction with iodine
monochloride because the products decomposed.
EXTENSION EXPERIMENT IN ORGANOTIN CHEMISTRY

Outline of the experiment

1) To prepare the Grignard reagent
Iodobenzene + Mg Benzyl Magnesium Iodide

2) To prepare organotin compound
Ph
2
SnCl
2
+ 2Benzyl Magnesium Iodide Dibenzyldiphenyltin

Preparation of Grignard reagent,
Benzyl Iodide + Mg Benzyl Magnesium Iodide

The reaction flask was dried thoroughly by using an oven.
The nitrogen gas was used to flush out the apparatus whilst the pressure equalizing
funnel was charged with a homogeneous solution of iodobenzene(4.28g,21mmol,1.5)
in dry diethyl ether (10 cm
3
). Magnesium turnings (0.50g,20mmol) were quickly
added through a wide-stem funnel and was covered with dry diethyl ether (10 cm
3
) .A
crystal of iodine was dropped carefully into the reaction flask. Stirring was not started
yet. 5 cm
3
of solution was added from the pressure equalizing funnel and the reaction
was started. The flask became warm when the bubbles appeared. The flask was
warmed to help the reaction by using a bowl of warm water. When the brown colour
of iodine decolourise , stirring was started. The iodomethane solution was added with
gentle refluxing.

Preparation of organotin compound ,
Ph
2
SnCl
2
+ 2Benzyl Magnesium Iodide Dibenzyldiphenyltin
At this time, nitrogen protection was no longer needed.
Dichlorodiphenyltin (2.5g,7.3mmol) was dissolved in dry diethyl ether (25 cm
3
)
and was added into the pressure equalizing funnel. The source heat was removed
from the flask and the stirring was maintained. The solution of tin compound was
added to the Grignard reagent in rate of droplets continuous stream. The addition
was completed approximately about 20 minutes. Stirring was continued futher for half
hour and was refluxed by using water bath at 60
o
C


Hydrolysis of excess Grignard reagent.
Aqueous ammonium chloride solution (10g/50 cm
3
) was added and two layers will be
formed. The mixture was stirred vigorously at this stage.

Isolation of organotin compound

The reaction flask was poured into a 250 cm
3
separating funnel and two layers were
observed. Note : The lower layer was the ammonium chloride solution. The ether
layer was collected and the aqueous layer was extracted by using diethyl ether ( 2 x
50 cm
3
). The combined ether layer was then extracted and was dried over
magnesium sulphate. Then,the dried ether layer was evaporated by using rotary
evaporator. Yellow oil of organotin compound was produced.

Results and analysis
Yield 0.5g,15%
NMR

Figure4.
1
H NMR of the dibenzyldiphenyltin


Analysis of the
1
H NMR

Chemical
shift(ppm)

Multiplicity

J(Hz)

Integration

Assignments

1.231

s - H
a
7.262

s - H
b







By principal there should be 4 peaks include the solvent used at 1.18ppm. There
should be like this
s
s
t

But I can see that there are 2 satellite spectra forming it should be three actually. The
satellite coupling constant that I got is 15 Hz and 22.3 Hz.
And the yield that I got is too small and I cant proceed and maybe is due to the
products being evaporated when I used the rotary evaporator thing. I only got a drop
of yellow oil.
My project didnt go well because I have to struggle to finish the core units because I
missed a week in the inorganic rotation due to the accident that I had and also I have
to repeat some of the expriments again and again. I do not have much time to finish
these projects. Sorry for the failure that I made.


Reference
1. personal.strath.ac.uk/m.d.spicer/docs/Experiment5.doc
2. http://144.206.159.178/ft/987/10702/205866.pdf
3. http://www.ncbi.nlm.nih.gov/pmc/articles/PMC1474848/pdf/envhper0
0501-0066.pdf
4. http://www.gelest.com/goods/pdf/Library/13Tin.pdf
5. http://homepage.smc.edu/kline_peggy/Organic/Lab_Reports_Ch_24/Che
m_24_Lab_Notes.html
6. http://www.google.com.my/imgres?q=kugelrohr+apparatus&hl=en&sa=
X&tbo=d&biw=1160&bih=568&tbm=isch&tbnid=P9NH25MzBKrukM:&i
mgrefurl=http://www.eplantscience.com/botanical_biotechnology_biolo
gy_chemistry/dean/vacuum_or_reducedpressure_distillation.php&docid=
9um2e1UGda1hOM&imgurl=http://www.eplantscience.com/botanical_bi
otechnology_biology_chemistry/dean/images/15.6.jpg&w=400&h=169&
ei=zzKvUNA6rqvQBaKLgPgI&zoom=1&iact=hc&vpx=443&vpy=218&dur
=10208&hovh=136&hovw=320&tx=193&ty=93&sig=109308800407616
143204&page=2&tbnh=106&tbnw=250&start=19&ndsp=25&ved=1t:429
,r:41,s:0,i:211