A reaction of tin tetra(N,N-diethylcarbamate) with phenylacetylene as a new route to tetra(phenylethynyl)tin

Article abstract of DOI:10.1007/s11172-014-0508-8

A reaction of tin tetra(N,N-diethylcarbamate) with phenylacetylene afforded tetra-(phenylethynyl)tin in 77% yield. The reaction can be promoted by Lewis acids.

Full text of DOI:10.1007/s11172-014-0508-8

Russian Chemical Bulletin, International Edition, Vol. 63, No. 3, pp. 775—776, March, 2014
775
A reaction of tin tetra(N,Nꢀdiethylcarbamate) with phenylacetylene
as a new route to tetra(phenylethynyl)tin
A. S. Levashov, A. A. Andreev, D. S. Buryi, and V. V. Konshin
Kuban State University,
1
49 ul. Stavropol´skaya, 350040 Krasnodar, Russian Federation.
Fax: +7 (861) 219 9571. Eꢀmail: organotin@mail.ru
A reaction of tin tetra(N,Nꢀdiethylcarbamate) with phenylacetylene afforded tetraꢀ
(
phenylethynyl)tin in 77% yield. The reaction can be promoted by Lewis acids.
Key words: tin tetra(N,Nꢀdiethylcarbamate), phenylacetylene, tetra(phenylethynyl)tin,
zinc chloride.
N,NꢀDialkylcarbamates of Group 14 elements are acꢀ
cessible reagents easily prepared either by aminocarboxyꢀ
product to decompose, thus considerably lowering its yield
(Table 1).
1
—5
lation of appropriate chlorides
or by carboxylation of
The reaction product was isolated by column chromaꢀ
tography on silica gel (silanized or dried in vacuo at 150 C)
and recrystallized from heptane under argon. The strucꢀ
ture of tetra(phenylethynyl)tin unambiguously determined
earlier by Xꢀray diffraction at an independently syntheꢀ
amines.1 They readily react with alcohols, ꢀdicarbonyl
compounds, and some C—H acids. Specifically, Oꢀsilylꢀ
and Oꢀstannylurethans1 have been used for the synthesis
of organosilicon and organotin derivatives of alkꢀ1ꢀynes.
The highest reactivity is exhibited by organotin derivatives
of carbamic acid.
,6
7
8
9
0
1
5
1
sized sample was confirmed by data from IR and H,
13
119
C, and Sn NMR spectroscopy, which agree well with
the literature data.
1
6,17
Tin tetra(N,Nꢀdialkylcarbamates) could be expected
to be suitable starting materials for the synthesis of tin
tetraalkynylides, which in turn are starting reagents for the
Stille reaction.1
The title reaction can be useful for the synthesis of
tetra(phenylethynyl)tin because it is free from the drawꢀ
backs of conventional organometallic routes to this comꢀ
1—14
1
8
18
We found that tin tetra(N,Nꢀdiethylcarbamate) reacts
with phenylacetylene even at room temperature: after 3 h,
the reaction mixture contains products in which one and
two carbamate groups are replaced by phenylethynyl ones
pound involving phenylethynyl reagents, sodium and
1
7
19
lithium alkynylides, or tetra(dialkylamino)stannanes.
Experimental
(
Sn –739.36 and –610.50, respectively); however, the sigꢀ
1
19
Solvents and starting reagents were thoroughly dried and
purified according to common procedures. All reactions were
nal due to tetra(phenylethynyl)tin is still absent ( Sn
NMR data). Replacement of all the four carbamate groups
occurs only above 100 C. Other factors facilitating the
forward reaction toward compound 3 include the use of
excess phenylacetylene and Lewis acids (e.g., zinc halides)
2
0
Table 1. Conditions of the alkynylation of tin tetra(N,Nꢀdiethylꢀ
carbamate) and the yields of compound 3
(
Scheme 1).
Ratio
of 1 : 2
Solvent
T/C
Lewis
acid
/h Yield
(%)
Scheme 1
1
1
1
1
1
1
1
1
1
1
: 4
: 4
: 6
: 6
: 6
: 6
: 6
: 6
: 6
: 6
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
80
110
110
110
80
—
—
—
ZnCl2
ZnCl2
ZnI2
ZnI2
ZnCl2
CdCl2
SnCl4
3
3
3
1.5
3
0.5
3
3
3
3
0
50
59
77
28
50
26
0
110
1,2ꢀDichloroethane 80
1,4ꢀDioxane
Toluene
Toluene
100
110
110
0
7
However, the use of stronger Lewis acids or prolonged
heating in the presence of such acids causes the target
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0775—0776, March, 2014.
066ꢀ5285/14/6303ꢀ0775 © 2014 Springer Science+Business Media, Inc.
1

776
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 3, March, 2014
Levashov et al.
carried out and the target compounds were isolated in an argon
atmosphere. H, C, and Sn NMR spectra were recorded on
3. N. A. Ryzhkova, A. A. Andreev, N. V. Komarov, Russ. Chem.
Bull. (Int. Ed.), 2007, 56, 546 [Izv. Akad. Nauk, Ser. Khim.,
2007, 525].
1
13
119
a JEOL ECA 400 instrument in CDCl (Aldrich) with reference
3
to the residual protons of the solvent. IR spectra were recorded
on a Shimadzu IR Prestige instrument.
4. USSR Inventor´s Certificate 1184246; Byull. Izobret. [Bulleꢀ
tin of Inventions], 2006, 11 (in Russian).
Tin tetra(N,Nꢀdiethylcarbamate) (1). A threeꢀneck flask
equipped with a stirrer, a reflux condenser, a gas inlet, and
a dropping funnel was charged with diethylamine (42 mL,
5. L. Abis, D. B. Dell´ Amico, F. Calderazzo, R. Caminiti,
F. Garbassi, S. Ianelli, G. Pelizzi, P. Robino, A. Tomei, J. Mol.
Catal. A: Chem., 1996, 108, Ll 13.
0
.4 mol) and toluene (100 mL). Carbon dioxide was bubbled
6. G. A. Horley, M. F. Mahon, K. C. Molloy, P. W. Haycock,
C. P. Myers, Inorg. Chem., 2002, 41, 5052.
through this mixture to saturation. Then SnCl (0.05 mol, 5.8 mL)
4
was slowly added dropwise. The reaction mixture was stirred at
7. N. V. Komarov, N. A. Ryzhkova, A. A. Andreev, Russ. Chem.
Bull. (Int. Ed.), 2004, 53, 936 [Izv. Akad. Nauk, Ser. Khim.,
2004, 898].
8. N. A. Boldyreva, N. V. Komarov, A. A. Andreev, J. Gen.
Chem. USSR (Engl. Transl.), 1988, 58, 1179 [Zh. Obshch.
Khim., 1988, 58, 1179].
9. V. V. Konshin, A. A. Andreev, N. V. Komarov, Tezisy doklaꢀ
dov IX Nauchnoi shkolyꢀkonferentsii po organicheskoi khimii
[Abstrs, IX Scientific SchoolꢀConf. on Organic Chemistry] (Deꢀ
cember 11—15, 2006, Moscow), Moscow, 2006, 201 (in Russian).
10. A. A. Andreev, N. A. Boldyreva, N. V. Komarov, J. Gen.
Chem. USSR (Engl. Transl.), 1986, 56, 1664 [Zh. Obshch.
Khim., 1986, 56, 1664].
11. J. K. Stille, Angew. Chem., Int. Ed., 1986, 25, 508.
12. V. Farina, V. Krishnamurthy, W. J. Scott, The Stille Reacꢀ
tion, Wiley and Sons, New York, 1998.
13. M. M. Heravi, E. Hashemi, F. Azimian, Tetrahedron, 2014,
70, 7.
14. RF Pat. 2439046; Byull. Izobret. [Bulletin of Inventions], 2012,
1 (in Russian).
15. M. Lahcini, M. T. Raisanen, P. M. Castro, M. Klinga,
M. Leskela, Acta Crystallogr., Sect. E, 2007, E63, m2762.
16. J. Lorberth, J. Organomet. Chem., 1969, 16, 327.
6
0 C for 1 h, cooled to 0 C, and kept for 2 h. The precipitate
that formed was filtered off. The filtrate was concentrated on
a rotary evaporator. The yield of a chlorideꢀfree product (a negative
Beilstein test) was 25 g (86%), m.p. 164 C (heptane—toluene,
–
1
4
(
: 1) (cf. Ref. 6: m.p. 120—121 C). IR (KBr), /cm : 1645
C=O); 1564, 1439 (COO); 1520 (C—N). 1H NMR (399.78
MHz, CDCl ), : 1.08 (t, 3 H, Me, J = 7 Hz); 3.31 (q, 2 H, CH ,
3
2
1
3
J = 7 Hz). C NMR (100.52 MHz, CDCl ), : 12.37, 41.83,
64.84. Sn NMR (149.08 MHz, CDCl ), : –930.34.
3
1
19
1
3
Tetra(phenylethynyl)tin (3). Phenylacetylene (0.66 mL,
6
mmol) and ZnCl (0.55 g, 4 mmol) were added to a solution of
2
tin tetra(N,Nꢀdiethylcarbamate) (0.56 g, 1 mmol) in toluene
10 mL). The reaction mixture was kept at 110 C for 1.5 h and
(
passed through a column packed with Kieselgel 60H silanisiert
silica gel (Merck). The eluate was concentrated on a rotary evapꢀ
orator. The residue was recrystallized from heptane. The yield of
product 3 was 0.40 g (77%), colorless needles, m.p. 174 C
1
(
cf. Ref. 18: m.p. 174 C). IR (KBr), /cm–1: 2152 (CC). H NMR
(
399.78 MHz, CDCl ), : 7.32—7.40 (m, 3 H); 7.59—7.61 (m, 2 H).
3
1
3
C NMR (100.52 MHz, CDCl ), : 85.45, 109.78, 122.18,
3
19
1
28.38, 129.37, 132.47. 1 Sn NMR (149.08 MHz, CDCl ),
3

: –332.29.
1
7. B. Wrackmeyer, G. Kehr, Main Group Met. Chem., 1993,
16, 305.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 12ꢀ03ꢀ31857
mol_a).
18. H. Hartmann, W. Reiss, B. Karbstein, Naturwissenschaften,
1959, 46, 321.
1
9. B. Wrackmeyer, G. Kehr, H. Zhou, Main Group Met. Chem.,
992, 15, 89.
1
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Received November 8, 2013;
in revised form March 4, 2014