DOI: 10.1126/science.263.5144.203. Free-Radical Side-Chain Bromination of Alkylaromatics in Supercritical Carbon Dioxide

Free-Radical Side-Chain Bromination of Alkylaromatics in Supercritical Carbon Dioxide

10.1126/science.263.5144.203

Crossref journal-article

American Association for the Advancement of Science (AAAS)

Science (221)

Abstract

Free-radical side-chain brominations of alkylaromatics in supercritical carbon dioxide (SC-CO 2 ) are reported. Direct bromination of toluene and ethylbenzene form the corresponding benzyl bromides in high yield. The observed selectivity in SC-CO 2 is similar to that observed in conventional organic solvents. Also, SC-CO 2 is an effective alternative to carbon tetrachloride for use in the classical Ziegler bromination with N -bromosuccinimide. Reaction yields are high, side products are minimized, and bromine-atom selectivities are observed. Thus, SC-CO 2 must be useful as a viable, environmentally benign substitute for many of the solvents typically used for free-radical reactions.

Bibliography

Tanko, J. M., & Blackert, J. F. (1994). Free-Radical Side-Chain Bromination of Alkylaromatics in Supercritical Carbon Dioxide. Science, 263(5144), 203â205.

Authors 2

James M. Tanko (first)
Joseph F. Blackert (additional)

References 22 Referenced 82

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ASANO, T, ACTIVATION AND REACTION VOLUMES IN SOLUTION, CHEMICAL REVIEWS 78: 407 (1978). (10.1021/cr60314a004) / CHEMICAL REVIEWS (1978)
BLACKERT J.F. unpublished data.
CHATEAUNEUT, E, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 115: 1915 (1993). (10.1021/ja00058a042) / JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (1993)
10.1126/science.257.5072.945
FRIEDRICH, S.S., SIDE-CHAIN BROMINATION OF ALPHA-SUBSTITUTED TOLUENES BY N-BROMOSUCCINIMIDE . A REVISION AND EXTENSION OF PREVIOUS OBSERVATIONS, JOURNAL OF ORGANIC CHEMISTRY 34: 900 (1969). (10.1021/jo01256a027) / JOURNAL OF ORGANIC CHEMISTRY (1969)
GUAN, Z, HOMOGENEOUS FREE-RADICAL POLYMERIZATIONS IN SUPERCRITICAL CARBON-DIOXIDE .2. THERMAL-DECOMPOSITION OF 2,2'-AZOBIS(ISOBUTYRONITRILE), MACROMOLECULES 26: 2663 (1993). (10.1021/ma00063a003) / MACROMOLECULES (1993)
ILLMAN, D, CHEMICAL & ENGINEERING NEWS 71: 5 (1993). / CHEMICAL & ENGINEERING NEWS (1993)
Johnston K. P. Supercritical Fluid Science and Technology (1989). (10.1021/bk-1989-0406)
LUNNING, U, TETRAHEDRON 41: 4289 (1985). (10.1016/S0040-4020(01)97200-X) / TETRAHEDRON (1985)
OSHEA, K. E., PHOTOCHEMISTRY AND PHOTOBIOLOGY 54: 571 (1991). (10.1111/j.1751-1097.1991.tb02058.x) / PHOTOCHEMISTRY AND PHOTOBIOLOGY (1991)
Poutsma, M. L., Free Radicals 2: 159 (1973). / Free Radicals (1973)
Ritchie C. D. Physical Organic Chemistry The Fundamental Concepts 2 74 (1990).
ROBERTS, C.B., UNIQUE PRESSURE EFFECTS ON THE ABSOLUTE KINETICS OF TRIPLET BENZOPHENONE PHOTOREDUCTION IN SUPERCRITICAL CO2, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 114: 8455 (1992). (10.1021/ja00048a016) / JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (1992)
Russell, G. A., Free Radicals 1: 275 (1973). / Free Radicals (1973)
Russell, G. A., Journal of the American Chemical Society 80: 4987 (1958). (10.1021/ja01551a056) / Journal of the American Chemical Society (1958)
RUSSELL, G.A., DIRECTIVE EFFECTS IN ALIPHATIC SUBSTITUTIONS .19. PHOTOBROMINATION WITH N-BROMOSUCCINIMIDE, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 85: 3139 (1963). (10.1021/ja00903a020) / JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (1963)
SIGMAN, M.E., SUPERCRITICAL CARBON-DIOXIDE .5. CARBOXYINVERSION REACTIONS OF DIACYL PEROXIDES - ALKYL GROUP REARRANGEMENT AND CO2 EXCHANGE, JOURNAL OF ORGANIC CHEMISTRY 52: 1754 (1987). (10.1021/jo00385a020) / JOURNAL OF ORGANIC CHEMISTRY (1987)
SUPPES, G.J., OXIDATION OF CUMENE IN SUPERCRITICAL REACTION MEDIA, INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH 28: 1152 (1989). (10.1021/ie00092a006) / INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH (1989)
Weast R. C. Handbook of Chemistry and Physics 55 (1974).
WEDIN, R.E., TODAYS CHEM WORK 2 4: 16 (1993). / TODAYS CHEM WORK (1993)
ZIEGLER, K, Halogenation of unsatiated substances in allyl addition, JUSTUS LIEBIGS ANNALEN DER CHEMIE 551: 80 (1942). (10.1002/jlac.19425510103) / JUSTUS LIEBIGS ANNALEN DER CHEMIE (1942)

Dates

Type	When
Created	18 years, 10 months ago (Oct. 5, 2006, 8:01 p.m.)
Deposited	1 year, 7 months ago (Jan. 12, 2024, 5:34 p.m.)
Indexed	1 year, 3 months ago (May 10, 2024, 4:27 a.m.)
Issued	31 years, 7 months ago (Jan. 14, 1994)
Published	31 years, 7 months ago (Jan. 14, 1994)
Published Print	31 years, 7 months ago (Jan. 14, 1994)

Funders 0

None

BibTeX

@article{Tanko_1994, title={Free-Radical Side-Chain Bromination of Alkylaromatics in Supercritical Carbon Dioxide}, volume={263}, ISSN={1095-9203}, url={http://dx.doi.org/10.1126/science.263.5144.203}, DOI={10.1126/science.263.5144.203}, number={5144}, journal={Science}, publisher={American Association for the Advancement of Science (AAAS)}, author={Tanko, James M. and Blackert, Joseph F.}, year={1994}, month=jan, pages={203–205} }

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