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The fixation of carbon dioxide with 1,2-epoxypropane catalyzed by alkali-metal halide in the presence of a crown ether
ELSEVIER
Inorganica Chimica Acta 257 ( 1997) 277-278
Note
The fixation of carbon dioxide with 1,2-epoxypropanecatalyzed by alkali-metal halide in the presenceof a crown ether Kuninobu Kasuga *, Naohiko Kabata Deportment
of Material
Science. Interdisciplinary
Faczdty
of Science and
Engineering. Shnane Universiry Matsue 690, Japan
Received 21 May 1996: revised 28 August 1996
Abstract
Cyclic carhonate was obtained from a chloroform as catalyst in the presence of a crown ether. Keywords:
solution of I ,Zepoxypropane
under carbon dioxide atmosphere using alkali-metal hakle
Carbon dioxide fixation; Crown ether; Alkali-meta! halide
1. Introduction
The chemical fixation of carbon dioxide has received much attention from the viewpoints of a carbon source in industry and an environmental problem [ l-31. There are four important industrial fixations of carbon dioxide: syntheses of urea, cyclic carbonate, salicylic acid, and methanol [ 4,5] +Syntheses of cyclic carbonate have been performed using catalysts suchasZnEt, [6],Ph$nI [7],Me,TeI, [7],orNal[8].In these cases, high temperature and/or high pressure of carbon dioxide were required. On the other hand, it has been reported that cyclic carbonate was prepared from a chloroform solution of epoxide catalyzed by tetraphenylporphyrinatoaluminum( III) or tetra-t-butylphthalocyaninatoaluminum( III) under carbon dioxide atmosphere at room temperahue
[%101* It is of interest to fix carbon dioxide with epoxide catalyzed by metal ions dissolved in chloroform using crown ether as a ligand instead of a macrocyclic one such as tetraphenylporphyrin or tetra-t-butylphthalocyanine. We report here that the cycloaddition of carbon dioxide was carried out with epoxide in chloroform at room temperature under a carbon dioxide atmosphere using alkali-metal s&s as the catalyst in the presence of a crown ether (Scheme 1) . 2. Experimental
2. I. Reagents As crown crownS-ether
ether, (B-15),
lScrownS-ether (n-15). benzo-1518-crownðer (u-18) and
* Corresponding author. 0020-1693/97/$17.00
0 1997 Elsevier Science S.A. All rights reserved
P/ISOO20-1693(96)05481-3
Scheme 1. The f~xadon of carbon dioxide witi EP.
dibenzo- 18-crown-6-ether (ID&18) were used without further purification. Alkali-metal halide, 1,2-epoxyprop-m (EP) and solvents were also used without further purification. 2.2. Measurements UV-Vis spectra were recorded on 3 Shim&u UV-3100 spectrophotometer. ‘H NMR spectra were measured with a JEOL GX270 spectrometer at 270 MHz. Gas chromatograms were measured with a Hewlett Packard 5890 Series II gas chromatograph. 2.3. Fixation
of carbon
dioxide
A chloroform solution (3 cm3) of EP (25-5 mm&), salt (1X10~3-6.2X10~‘mmo~)andcrownether(15X10~25 X lo-* mmol) was left to stand under carbon dioxide atmosphere at room temperature for I day. ‘The yield of propane- 1.,ZdioI carbonate (PDC) was estimated by means of a ‘H NMR spectrometer or a gas chromatograph using p chlorobenzaldehyde or naphthalene as the internal stand&, respe&ely.
K. Kasuga, N. Kabata/lnorganica
278
3. Results
Chimica Acta 257 (1997) 277-278 Table I The effect of the cation or anion of salts on the PDC yield ( x IO -4 mmol)
and 6lkclIssion
By the addition of sodium iodide to a chloroform solution of B-IS, the absorbance at 277 and 286 nm (shoulder) of the crown ether decreased,and a new band appeared at 273 nm. It is confirmed by the curve in Fig. 1 that the sodium cation formed a 1:1 type complex with B-15 consistent with the composition in the solid state [ 11] . On increasing the amount of sodium iodide added to a chloroform solution of B-15 and EP under carbon dioxide atmosphere, the yield of PDC increased due to the increase in the amount of chloroform-soluble complex (Fig. 2). A crown ether with a small hole such as n-15 or B-15 produced large amounts of PDC with the sodium cation, which has a small ionic radius, but scarcely produced PDC with a large-size ion such as rubidium or cesium becauseof the difficulty of complex formation (Table 1). A crown ether having a large-size hole such as n-18 formed a complex with all the alkali-metal ions, as elucidated by W spectral changes,and thus a large-size ion suchas rubidium or cesium also slightly produced PDC. With DB-18, the yield with rubidium or cesium was somewhat larger than that with the sodium. It is known that the large-size cation in the crownether complex is situated somewhat above the hole in the solid state [ 1l-l 31. The cation situated above the hole might then facilitate the formation of PDC, but the small sodium
Salt
nIS
B-15
n18
NaI N&r NaCl KI RbI Csl
53 4 4 14 11 3
48 21 9 8 5
IO
5
12 9 9
3 25 I9
[crownether] dm-‘.
=8.3 mmoldm-3.
[salt] =83 mmoldm-3,
DB-1%
[EP] =0.83mol
ion which sinks into the hole of DB-18 might decrease its activity. The yield of PDC decreased in the order of the iodide, the bromide, and the chloride (Table 1) . Furthermore, PDC was not prepared in the presence of a salt such as acetate,phosphate or carbonate. The salt with the halide was useful for the fixation, of which the salt with the iodide was the most suitable one. The yield (4.8 X lo-’ mmol) in dichloromethane was almost the same as that (5.3 X IO-’ mmol) in chloroform but was considerably decreased in benzene (2.3 X lo-’ mmol) due to the low solubility of carbon dioxide in benzene. PDC was not formed in methanol probably due to the fact that methanol competed with the crown ether for the cation, and then destabilized
the complex.
Acknowledgements
This work was supported by a Grant-in-Aid for Scientific ResearchNo. 06453050 from the Ministry of Education, Science, Sports and Culture and by a grant from the Electric Technology ResearchFoundation of Chugoku. 0.9 0
1.5 [;:I],
&l
Fig. 1. The absorbance at 287 nm vs. the concentration of sodium iodide in the presenceof B-15. [B-lS] =5 nun01 dmm3; ]Nal] -0-5.8 mm01 dm-“.
1.5 1-1
0 0
0 0.2
. 0.4
I 0.6
0.8
[Nat] I (B-IS] Ftg. 2. The relation of the PDC yield with the [sodium iodide]/[B-151 ratio. [B-15] = 16 mmoi dm-‘; [EP] = I .7 mol dm-‘.
References
[I 1S.tnoueand H. Koinuma.Rev.Inorg.Chem..6 ( 1984)291, [21 P. Bruunstein, D. Malt and D. Nobel.
Chem. Rev., 27 (1988) 747. [3] A. Behr. Angew. Chcm.. Inr. Ed. En@., 27 (1988) 661. [4] A. Behr, Chem. Ing. Tech.. 57 (1985) 893. IS] A. Behr. Chem. Eng. Techd, 10 (1987) 16. 161 S. Inoue, H. Koinumu and T. Tsuruta, J. Polym. Sci., Part B, 7 ( 1%7) 281. [7] R. Nomura. M. Kimura, S. Teshima, A. Ninagawa and H. Matsuda, Bull. Chem. Sot. Jpn., 55 (1982) 3200. [8] N. Kihara and T. Endo, Macromolecules, 25 ( 1992) 4824. 191 T. Aidaand S. lnoue, Ace. Chem. Rex, 29 ( 19%) 39, and Refs. therein. [ IO] K. Ka~ttga. S. Nagao. T. Fukumoto and M. Handa, Polyhedron, 15 ( 1995) 69; K. Kasuga, T. Kato. N. Kabata and M. Handa, Bull. Chem. Sm. Jpn.. 69 (1996) 2885. [I I ] M.A. Bush and M.R. Truter. J. Chem. Sot.. Perkin Trans. 11, ( 1972) 341. [I21 M.A. Bushattd M.R. Truter,J. Chem. Sot. B, (1971) 1440. 1131 P.R. Mallinson and M.R. Truter, J. Chem. Sot., Perkin Trans. 11, (1972)181.
Inorganica Chimica Acta 257 ( 1997) 277-278
Note
The fixation of carbon dioxide with 1,2-epoxypropanecatalyzed by alkali-metal halide in the presenceof a crown ether Kuninobu Kasuga *, Naohiko Kabata Deportment
of Material
Science. Interdisciplinary
Faczdty
of Science and
Engineering. Shnane Universiry Matsue 690, Japan
Received 21 May 1996: revised 28 August 1996
Abstract
Cyclic carhonate was obtained from a chloroform as catalyst in the presence of a crown ether. Keywords:
solution of I ,Zepoxypropane
under carbon dioxide atmosphere using alkali-metal hakle
Carbon dioxide fixation; Crown ether; Alkali-meta! halide
1. Introduction
The chemical fixation of carbon dioxide has received much attention from the viewpoints of a carbon source in industry and an environmental problem [ l-31. There are four important industrial fixations of carbon dioxide: syntheses of urea, cyclic carbonate, salicylic acid, and methanol [ 4,5] +Syntheses of cyclic carbonate have been performed using catalysts suchasZnEt, [6],Ph$nI [7],Me,TeI, [7],orNal[8].In these cases, high temperature and/or high pressure of carbon dioxide were required. On the other hand, it has been reported that cyclic carbonate was prepared from a chloroform solution of epoxide catalyzed by tetraphenylporphyrinatoaluminum( III) or tetra-t-butylphthalocyaninatoaluminum( III) under carbon dioxide atmosphere at room temperahue
[%101* It is of interest to fix carbon dioxide with epoxide catalyzed by metal ions dissolved in chloroform using crown ether as a ligand instead of a macrocyclic one such as tetraphenylporphyrin or tetra-t-butylphthalocyanine. We report here that the cycloaddition of carbon dioxide was carried out with epoxide in chloroform at room temperature under a carbon dioxide atmosphere using alkali-metal s&s as the catalyst in the presence of a crown ether (Scheme 1) . 2. Experimental
2. I. Reagents As crown crownS-ether
ether, (B-15),
lScrownS-ether (n-15). benzo-1518-crownðer (u-18) and
* Corresponding author. 0020-1693/97/$17.00
0 1997 Elsevier Science S.A. All rights reserved
P/ISOO20-1693(96)05481-3
Scheme 1. The f~xadon of carbon dioxide witi EP.
dibenzo- 18-crown-6-ether (ID&18) were used without further purification. Alkali-metal halide, 1,2-epoxyprop-m (EP) and solvents were also used without further purification. 2.2. Measurements UV-Vis spectra were recorded on 3 Shim&u UV-3100 spectrophotometer. ‘H NMR spectra were measured with a JEOL GX270 spectrometer at 270 MHz. Gas chromatograms were measured with a Hewlett Packard 5890 Series II gas chromatograph. 2.3. Fixation
of carbon
dioxide
A chloroform solution (3 cm3) of EP (25-5 mm&), salt (1X10~3-6.2X10~‘mmo~)andcrownether(15X10~25 X lo-* mmol) was left to stand under carbon dioxide atmosphere at room temperature for I day. ‘The yield of propane- 1.,ZdioI carbonate (PDC) was estimated by means of a ‘H NMR spectrometer or a gas chromatograph using p chlorobenzaldehyde or naphthalene as the internal stand&, respe&ely.
K. Kasuga, N. Kabata/lnorganica
278
3. Results
Chimica Acta 257 (1997) 277-278 Table I The effect of the cation or anion of salts on the PDC yield ( x IO -4 mmol)
and 6lkclIssion
By the addition of sodium iodide to a chloroform solution of B-IS, the absorbance at 277 and 286 nm (shoulder) of the crown ether decreased,and a new band appeared at 273 nm. It is confirmed by the curve in Fig. 1 that the sodium cation formed a 1:1 type complex with B-15 consistent with the composition in the solid state [ 11] . On increasing the amount of sodium iodide added to a chloroform solution of B-15 and EP under carbon dioxide atmosphere, the yield of PDC increased due to the increase in the amount of chloroform-soluble complex (Fig. 2). A crown ether with a small hole such as n-15 or B-15 produced large amounts of PDC with the sodium cation, which has a small ionic radius, but scarcely produced PDC with a large-size ion such as rubidium or cesium becauseof the difficulty of complex formation (Table 1). A crown ether having a large-size hole such as n-18 formed a complex with all the alkali-metal ions, as elucidated by W spectral changes,and thus a large-size ion suchas rubidium or cesium also slightly produced PDC. With DB-18, the yield with rubidium or cesium was somewhat larger than that with the sodium. It is known that the large-size cation in the crownether complex is situated somewhat above the hole in the solid state [ 1l-l 31. The cation situated above the hole might then facilitate the formation of PDC, but the small sodium
Salt
nIS
B-15
n18
NaI N&r NaCl KI RbI Csl
53 4 4 14 11 3
48 21 9 8 5
IO
5
12 9 9
3 25 I9
[crownether] dm-‘.
=8.3 mmoldm-3.
[salt] =83 mmoldm-3,
DB-1%
[EP] =0.83mol
ion which sinks into the hole of DB-18 might decrease its activity. The yield of PDC decreased in the order of the iodide, the bromide, and the chloride (Table 1) . Furthermore, PDC was not prepared in the presence of a salt such as acetate,phosphate or carbonate. The salt with the halide was useful for the fixation, of which the salt with the iodide was the most suitable one. The yield (4.8 X lo-’ mmol) in dichloromethane was almost the same as that (5.3 X IO-’ mmol) in chloroform but was considerably decreased in benzene (2.3 X lo-’ mmol) due to the low solubility of carbon dioxide in benzene. PDC was not formed in methanol probably due to the fact that methanol competed with the crown ether for the cation, and then destabilized
the complex.
Acknowledgements
This work was supported by a Grant-in-Aid for Scientific ResearchNo. 06453050 from the Ministry of Education, Science, Sports and Culture and by a grant from the Electric Technology ResearchFoundation of Chugoku. 0.9 0
1.5 [;:I],
&l
Fig. 1. The absorbance at 287 nm vs. the concentration of sodium iodide in the presenceof B-15. [B-lS] =5 nun01 dmm3; ]Nal] -0-5.8 mm01 dm-“.
1.5 1-1
0 0
0 0.2
. 0.4
I 0.6
0.8
[Nat] I (B-IS] Ftg. 2. The relation of the PDC yield with the [sodium iodide]/[B-151 ratio. [B-15] = 16 mmoi dm-‘; [EP] = I .7 mol dm-‘.
References
[I 1S.tnoueand H. Koinuma.Rev.Inorg.Chem..6 ( 1984)291, [21 P. Bruunstein, D. Malt and D. Nobel.
Chem. Rev., 27 (1988) 747. [3] A. Behr. Angew. Chcm.. Inr. Ed. En@., 27 (1988) 661. [4] A. Behr, Chem. Ing. Tech.. 57 (1985) 893. IS] A. Behr. Chem. Eng. Techd, 10 (1987) 16. 161 S. Inoue, H. Koinumu and T. Tsuruta, J. Polym. Sci., Part B, 7 ( 1%7) 281. [7] R. Nomura. M. Kimura, S. Teshima, A. Ninagawa and H. Matsuda, Bull. Chem. Sot. Jpn., 55 (1982) 3200. [8] N. Kihara and T. Endo, Macromolecules, 25 ( 1992) 4824. 191 T. Aidaand S. lnoue, Ace. Chem. Rex, 29 ( 19%) 39, and Refs. therein. [ IO] K. Ka~ttga. S. Nagao. T. Fukumoto and M. Handa, Polyhedron, 15 ( 1995) 69; K. Kasuga, T. Kato. N. Kabata and M. Handa, Bull. Chem. Sm. Jpn.. 69 (1996) 2885. [I I ] M.A. Bush and M.R. Truter. J. Chem. Sot.. Perkin Trans. 11, ( 1972) 341. [I21 M.A. Bushattd M.R. Truter,J. Chem. Sot. B, (1971) 1440. 1131 P.R. Mallinson and M.R. Truter, J. Chem. Sot., Perkin Trans. 11, (1972)181.