This article was downloaded by: [Tufts University]On: 27 October 2014, At: 09:45Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number: 1072954Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,UK

Synthesis and Reactivity inInorganic and Metal-OrganicChemistryPublication details, including instructions forauthors and subscription information:http://www.tandfonline.com/loi/lsrt19

The TransesterificationReaction of β-methoxycarbonylethyltinTrichloride and itsDimethylsulfoxide Adduct withAlcoholsLaijin Tian a , Zhengyu Zhou a , Bin Zhao a , WentaoYu b & Ping Yang ba Department of Chemistry , Qufu NormalUniversity , Qufu, Shandong, 273165, P. R. Chinab The State Key Laboratory of Crystal Materials ,Shandong University , Jinan, Shandong, 250100, P. R.ChinaPublished online: 23 Apr 2008.

To cite this article: Laijin Tian , Zhengyu Zhou , Bin Zhao , Wentao Yu & Ping Yang(2000) The Transesterification Reaction of β-methoxycarbonylethyltin Trichloride andits Dimethylsulfoxide Adduct with Alcohols, Synthesis and Reactivity in Inorganic andMetal-Organic Chemistry, 30:7, 1363-1372, DOI: 10.1080/00945710009351839

To link to this article: http://dx.doi.org/10.1080/00945710009351839

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all theinformation (the “Content”) contained in the publications on our platform.

However, Taylor & Francis, our agents, and our licensors make norepresentations or warranties whatsoever as to the accuracy, completeness,or suitability for any purpose of the Content. Any opinions and viewsexpressed in this publication are the opinions and views of the authors, andare not the views of or endorsed by Taylor & Francis. The accuracy of theContent should not be relied upon and should be independently verified withprimary sources of information. Taylor and Francis shall not be liable for anylosses, actions, claims, proceedings, demands, costs, expenses, damages,and other liabilities whatsoever or howsoever caused arising directly orindirectly in connection with, in relation to or arising out of the use of theContent.

This article may be used for research, teaching, and private study purposes.Any substantial or systematic reproduction, redistribution, reselling, loan,sub-licensing, systematic supply, or distribution in any form to anyone isexpressly forbidden. Terms & Conditions of access and use can be found athttp://www.tandfonline.com/page/terms-and-conditions

Dow

nloa

ded

by [

Tuf

ts U

nive

rsity

] at

09:

45 2

7 O

ctob

er 2

014

SYNTH. REACT. INORG. MET.-ORG. CHEM., 30(7), 1363-1372 (2000)

THE TFUNSESTEIUFICATION REACTION OF P-METHOXYCARBONYLETHYLTIN TRICHLORIDE AND ITS DIMETHYLSULFOXIDE ADDUCT WITH ALCOHOLS

Laijin Tian", Zhengyu Zhou", Bin Zhao", Wentao Yuh and Ping Yangb

a Department of Chemistry, Qufu Normal University, Qufu, Shandong 273165, P. R. China

Jinan, Shandong 250100, P. R. China The State Key Laboratory of Crystal Materials, Shandong University,

ABSTRACT

The transestcrification reaction of p-methoxycarbonylethyltin trichloride and

its dimethylsulfoxide adduct with alcohols is reported and the possible mechanism

is suggested. A series of p-alkoxycarbonylethyltin trichlorides and their dimethyl-

sulfoxide adducts were synthesized and characterized by means of elemental

analyses, IR and 'H NMR spectra and an X-ray single crystal dimaction study.

I"

P-Alkox ycarbonylethyl tin trichlorides, ROCOCH,CH,SnCl, (l), have attracted

considerable attention ever since their syntheses were first reported because of the

1363

Copyright Q 2000 by Marcel Dekker, Inc. www.dekker.com

Dow

nloa

ded

by [

Tuf

ts U

nive

rsity

] at

09:

45 2

7 O

ctob

er 2

014

1364 TlAN ET AL.

variety of coordination geometries about the tin atom and also their applicability as

PVC stabilizer with low mammalian toxicities'-9. The spectral data and crystal

structure (R = Me) determination of (1) show that the ROCOCH,CH, moiety acts

as a C, 0 chelating ligand in the solid state and non-coordinating solvents'.'.

However, the intramolecular coordination by the carbonyl oxygen of the ester

group can be broken by additional donor molecules'.'. In this paper, we report the

transesterification reaction of (1) (R = Me) and its dimethylsulfoxide adduct with

alcohols and the crystal structure of (1) (R = cyclohexyl).

S AND DISCUSSION

When P-methoxycarbonylethyltin trichloride (1 a) and its dimethylsulfoxide (L)

adduct (2a) are refluxed in an alcohol, they are readily converted into the

corresponding alkoxycarbonyl analogs with yields of 69-93%. The

transesterification reaction may be represented by the following equations:

CH,OCOCH,CH,SnCl, +ROH --+ ROCOCH2CH,SnCll 4- CHIOH

(1 4 (1 b)-(l k)

CH,OCOCH,CH,SnCl;L+ROH --+ ROCOCH,CH,SnCl;L + CH,OH

(2a) ( 2 b I - W

R = Me (a); Et (b); n-Pr (c); i-Pr (d); ally1 (e ) ; WBU ( f ) ; i-Bu (g);

isopentyl (h); cyclohexyl (i); isooctyl (j); benzyl (k).

The physical and analytical data of the compounds obtained are listed in Tables I

and 11. The 1R and ' I I NMR data of some of the ncw compounds are listed in Table

Dow

nloa

ded

by [

Tuf

ts U

nive

rsity

] at

09:

45 2

7 O

ctob

er 2

014

j3-METHOXYCARBONY LETHYLTlN TRlCHLORlDE 1365

Table I. Physical and Analytical Data for the Compounds (la)-(lk)

Compound Empirical Formula Yield

No. (Formula Weight) (%)

(1 a) C,H,CI,O,Sn 78.9

(1b) C,H,Cl,O,Sn 92.5

(1 c) C,H,,Cl,O,Sn 87.4

(1 4 C,H, ,Cl,O,Sn 63.2

(1 4 C,H,CI,O,Sn 90.2

(1 f) C,H,,CI,O,Sn 88.4

(1 g) C,H,,CI,O,Sn 86.0

(1h) C,H,,CI,O,Sn 78.6

(1 0 C,H,,C1,02Sn 72.3

(Ij) C,,H,,C1,02Sn 56.8

(1 k) C,,H,,C1,02Sn 68.5

(3 12.15)

(326.17)

(340.20)

(340.20)

(338.18)

(354.22)

(354.22)

(368.25)

(3 80.26)

(410.33)

(388.24)

M.P.~

67-69 (68) 59-60 (59)

(125)

(89)

(46)

(52)

124

89-90

46-48

52-53

67-68

161

21

140

Analysis, Found (Calculated)

C H Sn

15.50 2.13 37.86 (15.39) (2.26) (38.03)

18.16 2.62 35.98 (18.41) (2.78) (36.39)

21.03 3.18 34.55 (21.18) (3.26) (34.89)

21.22 3.12 34.61 (21.18) (3.26) (34.89)

21.36 2.58 34.96 (21.31) (2.68) (35.10)

23.68 3.62 33.61 (23.73) (3.70) (33.51)

23.56 3.55 33.38 (23.73) (3.70) (33.51)

25.74 3.89 32.28 (26.09) (4.11) (32.23)

28.40 3.96 31.24 (28.42) (4.00) (31.21)

31.96 5.19 28.76 (32.20) (5.16) (28.93)

30.91 2.75 30.61 (30.93) (2.86) (30.57)

a The numbers in parentheses are the melting points of the compounds obtained by the references 1 and 7 methods.

111. We attribute the occurrence of this novel transesterification to intramolecular

Lewis acid catalysis by the electrophilic SnCl, group. The coordination of the ester

carbonyl to tin atom'36 polarized the carbonyl bond, thereby making the carbonyl

carbon more susceptible to attack by a nucleophilic reagent such as alcohol. The

Dow

nloa

ded

by [

Tuf

ts U

nive

rsity

] at

09:

45 2

7 O

ctob

er 2

014

1366 TlAN ET AL.

Table 11. Physical and Analytical Data for the Compounds (2a)-(2k)

Compound Empirical Formula Yield M.P.~ Analysis, Found (Calculated)

No. (Formula Weight) (%) ("C) C H Sn C,H, ,Cl,O,SSn

(390.27)

C,H,,Cl,O,SSn (404.30)

C,H,,CI,O,SSn (418.33)

C,H I ,Cl,O,SS n (418.33)

C,H,,CI,O,SSn (416.31)

C,H ,,CI,O,SSn (432.36)

C,H,,Cl,O,SSn (43 2.3 6)

C,,H,,Cl,O,SSn (446.38)

C , ,H, , Cl,O,SSn (45 8.39)

C,,H,,CI,O,SSn (466.38)

83.0

92.3

87.6

78.3

90.4

83.8

86.8

78.8

74.4

72.1

119-120 (116-118)

9 1-92 (90-91 )

68-69 (68)

112-114

82-83 (82)

84-85 (81-82)

68-69 (67) 7 1-73

101-1 02

125-126

18.51 (18.46)

20.70 (20.79)

22.90 (22.97)

22.72 (22.97)

22.98 (23.08)

25.08 (25.00)

24.68 (25 .OO)

26.67 (26.91)

28.86 (2 8.82)

30.66 (30.90)

3.14 (3.33)

(3.74)

(4.10)

(4.10)

3.72

3.89

3.92

3.48 (3.63)

4.58 (4.43)

(4.43)

(4.74)

4.54 (4.62)

3.49 (3.67)

4.24

4.46

30.34 (30.41)

29.30 (29.3 6)

28.25 (28.37)

28.33 (28.37)

28.58 (28.51)

27.45 (27.43)

27.37 (27.43)

26.33 (26.60)

26.14 (25.89)

25.20 (25.45)

~ ~~

a The numbers in parentheses are the melting points of the compounds obtained by the references 6 and 7 methods.

possible mechanism for the transesterification is suggested in the Fig. I (reaction of

(la) with ROH as example). The transesterification with alcohols is useful to

transform easily available p-methoxycarbonylethyltin trichloride' and its

dimethylsulfoxide adduct6 into any otherwise less accessible P-alkoxycarbonyl-

cthyltin trichlorides and thcir dimcthylsulfoxide adducts. An analogous reaction,

Dow

nloa

ded

by [

Tuf

ts U

nive

rsity

] at

09:

45 2

7 O

ctob

er 2

014

P-METHOXYC ARBON Y LETHY LTlN TRI CHLORI DE 1367

Table 111. IR and 'H NMR Spectral Data for Some of the New Compounds

Compound IR (cm-', KBr) a 'H NMR (6, CDCl,)

v(C=O) v(S=O) CH,O/CHO COCH, CH,Sn L

(1 h) 1660 vs

(1 i) 1652 vs

(1j) 1658 vs

(1 k) 1649 vs

( 2 4 1648 vs 948 vs

652vs 953vs

648vs 950vs

(2k) 1650 vs 948 vs

4.22 t (6.5) 5.02 m

4.30 t (6.8) 5.41 s

5.18 ni

4.28 t (6.8)

5.04 m

5.40 s

3.01 t (7.5)

2.90 t (7.6)

(7.6)

(7.4)

2.88 t (7.2)

(7.4)

(7.4)

(7.4)

2.97 t

2.96 t

2.92 t

2.84 t

2.88 t

2.27 t (7.5)

2.20 t (7.6)

(7.6)

(7.4)

(7.2)

(7.4)

(7.4)

(7.4)

2.20 t

2.23 t

1.86 t 2.81 s

1.92 t 2.80 s

1.89 t 2.79 s

1.90 t 2.83 s

vs = very strong parentheses are the coupling constants in Hz.

m = multiplct, s = singlet, t = triplet. The numbers in

reaction of an amine to transform them into the corresponding amide, is currently

being examined.

Structure of (li) The molecular geometry and the atomic numbering scheme for (li) are shown

in Fig. 2, with selected bond lengths and bond angles given in Table IV. The

compound exists as a monomer which contains a five-member chelate ring, formed

via carbonyl oxygen to tin coordination. The structure of (li) is a distorted trigonal

bipyramid with two chlorines, Cl(2) and C1(3), and the alkyl C(l) in equatorial

Dow

nloa

ded

by [

Tuf

ts U

nive

rsity

] at

09:

45 2

7 O

ctob

er 2

014

1368 TIAN ET AL.

R&C -0-SnCl3 +--. RO-C =O-SnC13

Fig. 1. Possible Mechanism for the Transestenfication of (1 a)

Fig. 2 . Molecular Structure of (l i)

positions and the remaining chlorine CI(1) and oxygen 0(1) in axial sites. The

bond angles of C( 1)-Sn( l)-Cl(2), C( l)-Sn(l)-Cl(3), C1(2)-Sn( 1)-C1(3) and O( 1)-

Sn(l)-Cl(1) arc l25.93( l3), 120.70(13), 107.80(5) and 176.27(8)", respectively.

The axial Sn(1)-CI(1) bond length (2.3982(12) A) is longer than the equatorial

bonds Sn( 1)-C1(2) (2.3086( 13) A) and Sn( l)-CI(3) (2.321 8( 13) A). The structure of

(1 i) is very similar to the reported for ( 1 a)3. Comparisons of bond lengths for ( 1 i)

and ( la) are made i n Fig. 3. The Sn( 1)-O( 1) distance (2.362(3) A) in compound ( l i )

Dow

nloa

ded

by [

Tuf

ts U

nive

rsity

] at

09:

45 2

7 O

ctob

er 2

014

fi-METHOXYCARBONYLETHY LTlN TRICHLORIDE 1369

Table IV. Selected Bond Lengths (A) and Bond Angles (") for (li)

2.1 I9(4)

2.3086( 13)

2.362( 3)

1.5 1 l(6)

1.309(5)

1.500(6)

1.543(8)

1.486(9)

C( I)-Sn( 1)-C1(2)

C( l)-Sn(l)-Cl(3)

C1(2)-Sn( 1)-C1(3)

C( I)-Sn( 1)-O( 1)

C1(2)-Sn( 1)-O( 1)

C1(3)-Sn( 1)-O( 1)

C(1)-Sn(1)-Cl(l)

CI(Z)-Sn( 1)-Cl(1)

C1(3)-Sn( I)-CI(l)

O( 1)-Sn( I)-Cl( 1)

C(3)-0(2)-C(4)

C(3)-O( 1)-Sn( 1)

125.93( 13)

120.70( 13)

107.80(5)

76.81(13)

85.63( 8)

84.92( 8)

99.76( 11)

97.66(5)

95.70(5)

176.27(8)

119.1(3)

1 1 0.4(3)

2.3982( 12)

2.3218(13)

1.5 15(6)

1.21 5(5)

1.467(5)

1.501(7)

1.5 18(9)

1.536(7)

C(2)-C( I)-Sn( 1)

C(3)-C(2)-C( 1)

O( 1 )-C( 3)-O( 2)

O( 1)-C(3)-C(2)

0(2)-C(3)-C(2)

0(2)-C(4)-C(9)

0(2)-C(4)-C(5)

C(9)-C(4)-C(5)

C(4)-C(5)-C(6)

C(7)-C(G)-C(5)

C(8)-C(7)-C(6)

C(7)-C(8)-C(9)

11 1.2(3)

11 1.4(4)

124.5(4)

123.2(4)

112.3(4)

106.6(4)

109.2(4)

113.1(4)

110.3(4)

11 1.0(6)

11 1.2(5)

112.3(5)

is also comparable with the intramolecular Sn-0 distances in other octahcdral

ROCOCH2CH,Sn compounds (Sn-O,2.33-2.43 A)8,'o-'2.

EXPERIMENTAL

and P-

All chemicals were of reagent grade and were used without W h e r purification.

Dow

nloa

ded

by [

Tuf

ts U

nive

rsity

] at

09:

45 2

7 O

ctob

er 2

014

1370

Fig. 3. Comparison of Bond Lengths for (la) (data in parentheses) and (li).

p-Methoxycarbonylethyltin trichloridc and its diniethylsulfoxide adduct were

prepared according to literature procedures' '. Carbon. nitrogen and hydrogen

analyses were determined using a Pcrkin Elmer 2400 elemental analyser, and tin

was determined titrinictrically as Sn". Melting points were measured on a TX4-

lOOA microscopic melting point apparatus. 1R spectra were recorded on an Alpha

Centauri FT-IR spectrophotometcr using KBr discs in the range 4000-400 cm-l. ' I 1

hWR spectral data were collected using a Bruker AC-80 FT-NMR spectrometer

with CDCI, as solvent and 'rMS as internal standard.

on o f ( l & a d o

Solutions of (la) (3.12 g, 10 nimol) or (2a) (3.90 g, 10 nimol) dissolved in 60

mL ROH were refluxed for 2 h, and then concentrated to ccz. 10 m L by evaporation

under reduced pressure. The resultant white solid was recrystallized from

dichloronicthane-pctroleum ether (b.p. 30-60°C) ( 1 : 1 , v h ) . The yields and melting

points of the obtained compounds ((1 h)-(1 k) and (2b)-(2k)) are shown in Tables I

and TI.

Dow

nloa

ded

by [

Tuf

ts U

nive

rsity

] at

09:

45 2

7 O

ctob

er 2

014

j3-METHOXYCARBONYLETHY LTlN TRlCHLORlDE 1371

. . stal Structure D-

!&shUhhData. C,H,,CI,O,Sn, M = 380.25, monoclinic, space group f2,/c, a =

10.4443(9),b= 10.4823(7),c= 12.8113(11)~,a=90, p =90.953 (8) ,y=90° ,V=

1402.39(19) A', Z = 4, D, = 1.801 Mg m-,, F(000) = 744, p(Mo-K,) = 2.374 mm-',

h = 0.71073 A, T = 293(2) K.

Data C o l t . Intensity data for a

colorless crystal with dimensions 0.35~0.30~0.25 mm were measured on a Bruker

P4 four-circle diffractometer fitted with graphite monochromated Mo-K, radiation

(0.71073 A). A total of 5636 reflections were measured (-121 h 21, -121 k 212,

-152 1 215) using the 8-28 scan technique such that 28,, = 50.02' and of these,

2470 were independent (R,", = 0.0301) and 2128 were observed reflections

[1>2.00(1)]. The data were corrected for Lorentz and polarization effects and an

empirical absorption correction based on q~ scans was applied. The calculations

were performed using the Bruker XSCANS', program package.

The structure was solved and full-matrix least-squares refinement on F' was

performed using the Bruker SHELXTL ~ r o g r a m ' ~ . Anisotropic displacement

parameters were employed for non-H atoms and H-atoms were included in the

model at their calculated positions and refined isotropically. The weighting scheme

was w = l/[02(F,2)+(0.0530P)2 + 1.4037PI where P = (F;+2Fc2)/3. The refinement

converged to a final R[F2>20(FZ)] = 0.0316, wR(F2) = 0.0881, for 2128 unique

obscrvcd rcflections, S=1.087. The maximum and minimum heights of residual

electron density peak in the final difference map were 0.767 and -0.598 e ,k3, respectively. The maximum A h in the last refinement cycle was 0.000. Molecular

graphics were drawn with the program package Bruker SHELXTL".

ACKNOWLEDGEMENT

This work was supported by the State Key Laboratory of Crystal Materials and

the Natural Science Foundation of Shandong Province.

Dow

nloa

ded

by [

Tuf

ts U

nive

rsity

] at

09:

45 2

7 O

ctob

er 2

014

1372 TIAN ET AI,.

1. R. E. Hutton, J. W. Burley and V. Oakes, J. Organornet. Chern., U, 369 (1978).

2. P. G. Harrison, T. J. King and M. A. Healy, J. Organomet. Chem., 182, 17 (1979).

3. D. Maughan, J. L. Wardell and J. W. Burley, J. Organomet. Chem., U , 59 (1981).

4. D. K. Deb and A. K. Ghosh, Polyhedron, 5,863 (1986).

6. F. Fu, L. Tian, H. Pan, R. Willern and M. Gielcn, Bull. SOC. Chim. Belg., 99, 789 ( 1 990).

7 . L. Tian, S. Liu, S. Bi and F. FLI, Synth. React. lnorg. Met.-Org. Chem., 22, 127 (1 997).

8. I,. Tian, Z. Zhou, B. Zhao and W. YLI, Polyhedron, E, 1275 (1 998).

9. T. G Kugele, Bclg. Pat. 864, 976 (1978): Chcni. Abstr., 2.0, 104943J (1979).

10. L. Tian, Z. Zhou, B. Zhao, and C. Zhang, Main Group Met. Chern., 21, 735 ( 1 998).

11. L. l ian, F. Fu, D. Zhu. I I . Pan, Y. Xing and Y. Lin, .4cta Chini. Sinica, 55, 884 (1997); Chem. Abstr., 121,307436b (1997).

12. 0.-S. Jung, J. H. Jeong and Y. S. Sohn, Polyhedron, 8, 1413 (1989).

13. Bruker, XSCANS Uscr’s Manual, Version 2.1, Bruker Axs Inc., Madison, Wisconsin, USA (1996).

14. Bruker, SIIELXTL, “Structure Determination Programs”, Version 5.1, Brukcr A x s Inc., Madison, Wisconsin, USA (1997).

Received 22 January 2ooo Referee I: E. J . Kupchik Accepted: 25 April 2000 Referee 11: J . H. Thayer

Dow

nloa

ded

by [

Tuf

ts U

nive

rsity

] at

09:

45 2

7 O

ctob

er 2

014