The Journal of Organic Chemistry
Article
60 °C for 24 or 72 h after which time the pressure was released and
the autoclave was opened. The reaction mixture was dissolved in
dichloromethane (3 mL) and passed through a glass Pasteur pipet half
filled with silica to remove the catalyst and Bu4NBr which are retained
on the surface of the silica. The eluent was evaporated, and the residue
was triturated with petroleum ether to crystallize cyclic carbonate 6a−
e as a white solid or to leave the product as an oil.
4.7. Synthesis of cis-Cyclohexane-1,2-diol55,57 7b. To cyclic
carbonate 6b (42.6 mg, 0.3 mmol) were added methanol (20 mL) and
conc. hydrochloric acid (5 mL). The resulting solution was heated at
reflux for 24 h, cooled, and then evaporated to dryness using ethanol
to form an azeotrope with the water. The residue was washed with
cold petroleum ether and then dried under vacuum to give diol 7b as a
white solid in 86% yield. Mp 90−94 °C (lit.57 93−95 °C), νmax(ATR)
3256, 2930, 2865, 1440, 1364, and 1073 cm−1; δH(CDCl3) 1.3−1.4
(4H, br), 1.6−1.7 (2H, br), 1.8−1.9 (2H, br), 1.98 (2H, s); 3.7−4.0
(2H, br); δC(CDCl3) 21.5, 30.2, 70.7.
trans-1,2-Diphenylethylene Carbonate 6a.47 Mp 112−118 °C
(lit.47 110−111 °C); νmax(ATR) 3030, 2964, 1815, and 1458 cm−1;
δH(CDCl3) 5.45 (2H, s), 7.3−7.4 (4H, m), 7.4−7.5 (6H, m);
δC(CDCl3) 85.3, 126.1, 129.3, 129.8, 135.3, 153.9; GCMS tR 14.86
min; m/z(CI) 241 (MH+, 12), 196 (100), 178 (25), 167 (60), 105
(55), 89 (75).
ASSOCIATED CONTENT
■
S
* Supporting Information
cis-1,2-Cyclohexene Carbonate 6b.49 Mp 35−37 °C (lit.51 34−35
°C); νmax(ATR) 2946, 2869, and 1788 cm−1; δH(CDCl3) 1.4−1.5 (2H,
m), 1.6−1.7 (2H, m), 1.9−2.0 (4H, m), 4.6−4.7 (2H, m); δC(CDCl3)
19.0, 26.7, 75.6, 155.1.
1H and 13C NMR and GCMS spectra for cyclic carbonates; 1H
and 13C NMR spectra for epoxides 5a−e and diols 7a−d. This
material is available free of charge via the Internet at http://
cis-1,2-Cyclopentene Carbonate 6c.50,51 Mp 30−33 °C (lit.50 29−
30 °C); νmax(ATR) 2956, 2885, and 1792 cm−1; δH(CDCl3) 1.5−1.9
(4H, m), 2.1−2.3 (2H, m), 5.0−5.2 (2H, m); δC(CDCl3) 21.5, 33.1,
81.7, 155.2; GCMS tR 8.38 min; m/z(CI) 129 (MH+, 17), 83 (17), 55
(100), 41 (25).
AUTHOR INFORMATION
Corresponding Author
■
cis-2,3-Butene Carbonate 6d.47 Obtained as a pale yellow oil;
νmax(ATR) 2939, 2881, and 1791 cm−1; δH(CDCl3) 1.32 (6H, d J 6.1
Hz), 4.7−4.9 (2H, m); δC(CDCl3) 14.3, 76.0, 154.5; GCMS tR 6.52
min; m/z(CI) 117 (MH+, 25), 43 (100).
Present Address
†Departamento de Activacion
de Enlaces por Complejos
́
́ ́
́ ́
icos, Instituto de Sintesis Quimica y Catalisis
Organometal
Homogenea (ISQCH), CSIC-Universidad de Zaragoza, Pedro
2-Methylpropene Carbonate 6e.59 Obtained as a pale yellow oil;
νmax(ATR) 2960, 2812, and 1784 cm−1; δH(CDCl3) 1.51 (6H, s), 4.14
(2H, s); δC(CDCl3) 26.2, 75.5, 81.8, 154.7; GCMS tR 7.17 min; m/
z(CI) 117 (MH+, 100), 86 (26), 55 (28), 43 (68).
́
Cerbuna 12, 50009, Zaragoza, Spain.
Notes
The authors declare no competing financial interest.
4.5. General Procedure for the Synthesis of Cyclic
Carbonates 4a−h Using Compressed Air. Epoxide 3a−h (0.1
mmol), catalyst 1 (2.8 mg, 2.5 × 10−3 mmol), and Bu4NBr (0.75 mg,
2.5 × 10−3 mmol) were added to a glass vial fitted with a stirrer bar.
The vial was placed in an autoclave, pressurized to 25 bar with
compressed air, and heated to 50 °C. The reaction was stirred under
these conditions for 24 h, then the reactor was cooled using an
acetone/dry ice bath, and the pressure was released. The reaction
mixture was analyzed by 1H NMR spectroscopy to determine the
conversion of epoxide 3a−h into cyclic carbonate 4a−h. In the case of
epoxide 3c, this procedure was carried out a total of 8 times and the
reaction mixtures combined to give sufficient material to purify by flash
chromatography (eluting with hexane/EtOAc, 8:1 to 1:1) to give
cyclic carbonate 4c (107.0 mg, 67%) as a colorless oil. νmax(ATR)
2926, 2856, and 1834 cm−1; δH(CDCl3) 0.89 (3H, t J 6.9 Hz), 1.2−1.6
(12H, m), 1.6−1.75 (1H, m), 1.75−1.9 (1H, m), 4.07 (1H, dd J 8.3,
7.4 Hz), 4.53 (1H, t J 8.1 Hz), 4.71 (1H, ddd J 13.0, 7.7, 5.5 Hz);
δC(CDCl3) 14.0, 22.6, 24.4, 29.0, 29.1, 29.3, 31.8, 33.9, 69.4, 155.0;
GCMS tR 13.48 min; m/z(CI) 201 (MH+, 50), 95 (55), 81 (100).
4.6. General Procedure for the Synthesis of Diols 7a,c,d. To
cyclic carbonate 6a−c (0.3 mmol) in a round bottomed flask were
added 5 M aqueous KOH (20 mL) and THF (10 mL). The resulting
solution was refluxed for 3 h, then cooled to room temperature, and
extracted with CH2Cl2 (3 × 20 mL). The organic layers were
combined and washed with 1 M aq. HCl (60 mL). The organic layer
was dried (Na2SO4) and evaporated to dryness to leave diols 7a,c,d.
trans-1,2-Diphenylethan-1,2-diol 7a.54−56 Obtained as a white
solid in 90% yield. Mp 145−149 °C (lit.56 150 °C), νmax(ATR) 3270
and 1454 cm−1; δH(CDCl3) 4.70 (2H, s), 7.0−7.1 (4H, m), 7.1−7.2
(6H, m); δC(CDCl3) 78.8, 127.2, 127.7, 128.0, 140.8.
ACKNOWLEDGMENTS
The authors thank Newcastle University for financial support.
■
REFERENCES
■
(1) Aresta, M.; Dibenedetto, A. Dalton Trans. 2007, 2975.
(2) Yu, K. M. K.; Curcic, I.; Gabriel, J.; Tsang, S. C. E. ChemSusChem.
2008, 1, 893.
(3) Aresta, M., Ed. Carbon Dioxide as Chemical Feedstock; Wiley-
VCH: Weinheim, 2010; pp 1−375.
(4) Styring, P.; Armstrong, K. Chem. Today 2011, 29, 28.
(5) Schrag, D. P. Science 2007, 315, 812.
(6) North, M. Chem. Today 2012, 30 (3 May/June: Monographic
supplement: Catalysis applications), 3.
(7) Darensbourg, D. J. Inorg. Chem. 2010, 49, 10765.
(8) Kember, M. R.; Buchard, A.; Williams, C. K. Chem. Commun.
2011, 47, 141.
(9) North, M.; Pasquale, R.; Young, C. Green Chem. 2010, 12, 1514.
(10) Decortes, A.; Castilla, A. M.; Kleij, A. W. Angew. Chem., Int. Ed.
2010, 49, 9822.
(11) Clements, J. H. Ind. Eng. Chem. Res. 2003, 42, 663.
(12) Schaffner, B.; Schaffner, F.; Verevkin, S. P.; Borner, A. Chem.
̈
̈
̈
Rev. 2010, 110, 4554.
(13) Xu, K. Chem. Rev. 2004, 104, 4303.
(14) Etacheri, V.; Marom, R.; Elazari, R.; Salitra, G.; Aurbach, D.
Energy Environ. Sci. 2011, 4, 3243.
(15) North, M.; Pizzato, F.; Villuendas, P. ChemSusChem 2009, 2,
862.
cis-Cyclopentane-1,2-diol 7c:.55,57 Obtained as a white solid in
45% yield. Mp 28−31 °C (lit.57 28−29 °C), νmax(ATR) 3361, 1338,
and 1035 cm−1; δH(CDCl3) 1.0−2.2 (8H, m), 3.9−4.2 (2H, br);
δC(CDCl3) 19.9, 31.5, 74.0.
(16) North, M.; Villuendas, P. Org. Lett. 2010, 12, 2378.
(17) Clegg, W.; Harrington, R. W.; North, M.; Pizzato, F.; Villuendas,
P. Tetrahedron: Asymmetry 2010, 21, 1262.
(18) Morcillo, M.; North, M.; Villuendas, P. Synthesis 2011, 1918.
(19) Beattie, C.; North, M.; Villuendas, P. Molecules 2011, 16, 3420.
(20) Peppel, W. J. Ind. Eng. Chem. 1958, 50, 767.
(21) Fukuoka, S.; Kawamura, M.; Komiya, K.; Tojo, M.; Hachiya, H.;
Hasegawa, K.; Aminaka, M.; Okamoto, H.; Fukawa, I.; Konno, S.
Green Chem. 2003, 5, 497.
trans-Cyclohexane-1,2-diol 7d.55,57 The initially formed 1:3
mixture of diols 7b and 7d was recrystallized from petroleum ether
to give diol 7d as a white solid in 46% yield. Mp 105−108 °C (lit.60
105−107 °C), νmax(ATR) 3276, 2932, 2859, 1444, and 1065 cm−1;
δH(CDCl3) 1.2−1.4 (4H, m), 1.6−1.8 (2H, m), 1.9−2.1 (2H, m), 2.20
(2H, s), 3.3−3.4 (2H, m); δC(CDCl3) 24.4, 33.0, 76.0.
(22) Yoshida, M.; Ihara, M. Chem.Eur. J. 2004, 10, 2886.
425
dx.doi.org/10.1021/jo302317w | J. Org. Chem. 2013, 78, 419−426