Acids are the most common industrial catalysts but have the disadvantage of requiring post-reaction neutralization and salt disposal. We show the catalytic use of self-neutralizing acids. Carbon dioxide interacts with water and amines to form carbonic acid and carbamates. A similar interaction occurs with alcohols to form alkylcarbonic acids. All three solvent systems provide in situ acid formation for catalysis which can be easily neutralized by removal of carbon dioxide. However, water has poor organic solubility and amines form salts so only alkylcarbonic acids combine good organic solubility with simple neutralization via depressurization. The use of in situ acid also completely eliminates the solid salt wastes associated with many acid processes. To elucidate how to implement these systems in place of a standard acid system we compare the reaction rates of several alkylcarbonic acids with diazodiphenylmethane (DDM). We report also the effect of CO2 pressure on reaction rate of DDM as well as measure the dielectric constant of these systems. Finally, a Hammett plot is used to identify the dominant step in alkylcarbonic acid catalysis.
Similar content being viewed by others
References
M. Eissen J.O. Metzger (2002) Chem. Eur. J. 8 3580 Occurrence Handle1:CAS:528:DC%2BD38Xmslequr0%3D Occurrence Handle10.1002/1521-3765(20020816)8:16<3580::AID-CHEM3580>3.0.CO;2-J
C.A. Eckert D. Bush J.S. Brown C.L. Liotta (2000) Ind. Eng. Chem. Res. 39 4615 Occurrence Handle1:CAS:528:DC%2BD3cXosVehtLo%3D Occurrence Handle10.1021/ie000396n
C.A. Eckert K. Chandler (1998) J. Supercritical Fluids 13 187 Occurrence Handle1:CAS:528:DyaK1cXltFKitLg%3D Occurrence Handle10.1016/S0896-8446(98)00051-5
C.A. Eckert B.L. Knutson P.G. Debenedietti (1996) Nature 383 313 Occurrence Handle1:CAS:528:DyaK28XlvFaisbw%3D Occurrence Handle10.1038/383313a0
M. Wei G.T. Musie D.H. Busch B. Subramaniam (2001) J. Am. Chem. Soc. 124 2513 Occurrence Handle10.1021/ja0114411
G.T. Musie M. Wei D.H. Busch B. Subramaniam (2001) Coor. Chem. Rev. 219–221 789 Occurrence Handle10.1016/S0010-8545(01)00367-8
L.A. Blanchard J.F. Brennecke (2001) Green Chem. 3 17 Occurrence Handle1:CAS:528:DC%2BD3MXps1Slug%3D%3D Occurrence Handle10.1039/b007734h
C.J. Chang A.D. Randolph (1990) AICHE J. 36 939 Occurrence Handle1:CAS:528:DyaK3cXks1aitr4%3D Occurrence Handle10.1002/aic.690360615
C. Lin G. Muhrer M. Mazzotti B. Subramaniam (2003) Ind. Eng. Chem. Res. 42 2171 Occurrence Handle1:CAS:528:DC%2BD3sXivFGntLw%3D Occurrence Handle10.1021/ie020784k
X. Xie, J.S. Brown, P.J. Joseph, C.L. Liotta and C.A. Eckert, Chem. Commun. (2002) 1156.
J. Zhao S.V. Olesik (2001) Anal. Chim. Acta 449 221 Occurrence Handle1:CAS:528:DC%2BD3MXoslKgs7Y%3D Occurrence Handle10.1016/S0003-2670(01)01337-X
K.N. West C. Wheeler J.P. McCarney K.N. Griffith D. Bush C.L. Liotta C.A. Eckert (2001) J. Phys. Chem. A 105 3947 Occurrence Handle1:CAS:528:DC%2BD3MXit12htL8%3D
X. Xie C.L. Liotta C.A. Eckert (2004) Ind. Eng. Chem. Res. 43 2605 Occurrence Handle1:CAS:528:DC%2BD2cXjsVChsL8%3D Occurrence Handle10.1021/ie034103c
T.S. Chamblee R.R. Weikel S.A. Nolen C.L. Liotta C.A. Eckert (2004) Green Chem. 6 382 Occurrence Handle1:CAS:528:DC%2BD2cXnsVyjtb0%3D Occurrence Handle10.1039/b400393d
R.R. Weikel, C.L. Liotta and C.A. Eckert, Green Chem. (submitted).
C. Hulme L. Ma J.J. Romano G. Morton S.-Y. Tang M.-P. Cherrier S. Choi J. Salvino R. Labaudiniere (2000) Tetrahedron Lett. 41 1889 Occurrence Handle1:CAS:528:DC%2BD3cXit1Krt7w%3D Occurrence Handle10.1016/S0040-4039(00)00053-8
T.A. Keating R.W. Armstrong (1998) J. Org. Chem. 63 867 Occurrence Handle1:CAS:528:DyaK1cXkvVWrsw%3D%3D Occurrence Handle10.1021/jo971463z
A. Buckley N.B. Chapman M.R.J. Dack J. Shorter H.M. Wall (1968) J. Chem. Soc. B 2 631 Occurrence Handle10.1039/j29680000631
R.A. Dombro M.A. McHugh G.A. Prentice C.R. Westgate (1991) Fluid Phase Equilib. 61 227 Occurrence Handle1:CAS:528:DyaK3MXhsFGisrc%3D Occurrence Handle10.1016/0378-3812(91)80001-C
V. Roskar R.A. Dombro G.A. Prentice C.R. Westgate M.A. McHugh (1992) Fluid Phase Equilib. 77 241 Occurrence Handle1:CAS:528:DyaK3sXntFClsQ%3D%3D Occurrence Handle10.1016/0378-3812(92)85106-I
D.L. Golfarb D.P. Fernandez H.R. Corti (1999) Fluid Phase Equilib. 158–160 1011 Occurrence Handle10.1016/S0378-3812(99)00146-6
S.B. Lee R.L. Smith H. Inomata K. Arai (2000) Rev. Sci. Instruments 71 4226 Occurrence Handle1:CAS:528:DC%2BD3cXnslygsLk%3D Occurrence Handle10.1063/1.1321303
L.I. Smith K.L. Howard (1955) Org. Synth. Collection 3 351
C.J. Chang K.-L. Chiu D. Chang-Yih (1998) J. Supercritical Fluids 12 223 Occurrence Handle10.1016/S0896-8446(98)00076-X
F.A. Carroll (1998) Perspectives on Structure and Mechanism in Organic Chemistry Brooks/Cole Publishing Company Pacific Grove, CA 384
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Weikel, R.R., Hallett, J.P., Liotta, C.L. et al. Self-neutralizing in situ Acid Catalysts from CO2. Top Catal 37, 75–80 (2006). https://doi.org/10.1007/s11244-006-0007-8
Issue Date:
DOI: https://doi.org/10.1007/s11244-006-0007-8