Organic Process Research & Development
Article
(14) For extensive treatises on microreactor and continuous flow
technology, see: (a) Flow Chemistry; Darvas, F., Hessel, V., Dorman,
G., Eds.; De Gruyter:Berlin, 2014. (b) Microreactors in Preparative
Chemistry; Reschetilowski, W., Ed.; Wiley-VCH: Weinheim, Germany,
2013. (c) Microreactors in Organic Synthesis and Catalysis, 2nd ed.;
Wirth, T., Ed.; Wiley-VCH: Weinheim, Germany, 2013. (d)
Handbook of Micro Reactors; Hessel, V., Schouten, J. C., Renken, A.,
Wang, Y., Yoshida, J.-i., Eds.; Wiley-VC: Weinheim, Germany, 2009.
(e) Chemical Reactions and Processes under Flow Conditions; Luis, S. V.,
Garcia-Verdugo, E., Eds.; RSC Green Chemistry, 2010.
Additional experimental information, supplementary
1
figures, and copies of H NMR and 13C NMR spectra
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
(15) For recent reviews on flow chemistry, see: (a) Gutmann, B.;
Cantillo, D.; Kappe, C. O. Angew. Chem., Int. Ed. 2015, 54, 6688−
6728. (b) Jensen, K. F.; Reizman, B. J.; Newman, S. G. Lab Chip 2014,
14, 3206−3212. (c) Wiles, C.; Watts, P. Green Chem. 2014, 16, 55−62.
(d) Newman, S. G.; Jensen, K. F. Green Chem. 2013, 15, 1456−1472.
(e) Baxendale, I. R.; Brocken, L.; Mallia, C. J. Green Process. Synth.
2013, 2, 211−230. (f) McQuade, D. T.; Seeberger, P. H. J. Org. Chem.
2013, 78, 6384−6389. (g) Pastre, J. C.; Browne, D. L.; Ley, S. V.
Chem. Soc. Rev. 2013, 42, 8849−8869.
ACKNOWLEDGMENTS
■
The authors gratefully thank Dr. David Cantillo for providing
computational calculations. We thank NAWI Graz financial
support.
REFERENCES
■
(16) Hamano, M.; Nagy, K. D.; Jensen, K. F. Chem. Commun. 2012,
48, 2086−2088 and references therein..
(1) International Narcotics Control Board (INCB), Narcotic Drugs
Report 2013: Estimated World Requirements for 2014, Statistics for 2012;
United Nations Publication: New York, 2014. Available via the
(March 13, 2015).
(2) McGrath, N. A.; Brichacek, M.; Njardarson, J. T. J. Chem. Educ.
2010, 87, 1348−1349.
(3) Karch, S. B., Ed. Pharmacokinetics and pharmacodynamics of
abused drugs; CRC Press: Boca Raton, 2007.
(4) (a) Black, T. H.; Forsee, J. C.; Probst, D. A. Synth. Commun.
2000, 30, 3195−3201. (b) Rapoport, H.; Naumann, R.; Bissell, E. R.;
Bonner, R. M. J. Org. Chem. 1950, 15, 1103−1107. (c) Pfister, K.;
Tishler, M. Process of preparing dihydrocodeinone. US 2715626A,
1955.
(5) (a) Wang, P. X.; White, C. R. Method for the catalytic production
of hydrocodone and hydromorphone. US 7323565B2, 2008.
(b) Wang, P. X.; Jiang, T.; Berberich, D. W. Preparation of saturated
ketone morphinan compounds by catalytic isomerization. WO 2010/
118271 A1, 2010. (c) Gindelberger, D. E. Heterogeneous ruthenium
metal catalyst for the production of hydrocodone, hydromorphone or
a derivative thereof. US 8383815B2, 2013. (d) Wang, P. X.; Jiang, T.;
Berberich, D. W.; Gurusamy, N.; Jung, C. K. Preparation of saturated
ketone morphinane compounds. WO 2010118275, 2010.
(6) (a) Mudryk, B.; Kant, J.; Sapino, C. Preparation of narcotic
(17) (a) Pieber, B.; Martinez, S. T.; Cantillo, D.; Kappe, C. O. Angew.
Chem., Int. Ed. 2013, 52, 10241−10244. (b) Pieber, B.; Glasnov, T.;
Kappe, C. O. Chem. - Eur. J. 2015, 21, 4368−4376.
(18) For a recent review on Novel Process Windows, see: Hessel, V.;
Kralisch, D.; Kockmann, N.; Noel, T.; Wang, Q. ChemSusChem 2013,
6, 746−789.
(19) (a) Lamani, M.; Ravikumara, G. S.; Prabhu, K. R. Adv. Synth.
Catal. 2012, 354, 1437−1442. (b) Kim, E.; Kim, S.; Kim, B.; Bull, M.
Bull. Korean Chem. Soc. 2011, 32, 3183−3186. (c) Jang, Y.; Kim, S.;
Jun, S. W.; Kim, B. H.; Hwang, S.; Song, I. K.; Kim, B. M.; Hyeon, T.
Chem. Commun. 2011, 47, 3601−3603.
(20) (a) Imada, Y.; Iida, H.; Naota, T. J. Am. Chem. Soc. 2005, 127,
14544−14545. (b) Smit, C.; Fraaije, M. W.; Minnaard, A. J. J. Org.
Chem. 2008, 73, 9482−9485. (c) Marsh, B. J.; Heath, E. L.; Carbery,
D. R. Chem. Commun. 2011, 47, 280−282. (d) Teichert, J. F.; den
Hartog, T.; Hanstein, M.; Smit, C.; ter Horst, B.; Hernandez-Olmos,
V.; Feringa, B. L.; Minnaard, A. J. ACS Catal. 2011, 1, 309−315.
(e) Imada, Y.; Iida, H.; Kitagawa, T.; Naota, T. Chem. - Eur. J. 2011,
17, 5908−5920. (f) Lamani, M.; Guralamata, R. S.; Prabhu, K. R.
Chem. Commun. 2012, 48, 6583−6585.
(21) Leow, D.; Chen, Y.-H.; Hung, T.-H.; Su, Y.; Lin, Y.-Z. Eur. J.
Org. Chem. 2014, 2014, 7347−7352.
(22) For catalyst-free examples in batch, see: (a) Menges, N.; Balci,
M. Synlett 2014, 25, 671−676. (b) Chen, H.; Wang, J.; Hong, X.;
Zhou, H.-B.; Dong, C. Can. J. Chem. 2012, 90, 758−761. (c) Santra, S.;
Guin, J. Eur. J. Org. Chem. 2015, 2015, 7253−7257.
analgesics. WO 1998005667A1, 1998. (b) Gom
P.; Backvall, J.-E.; Martín-Matute, B. RSC Adv. 2014, 4, 39519−39522.
́
ez, A. B.; Holmberg,
̈
(7) (a) Fist, A. J.; Byrne, C. J.; Gerlach, W. L. Production of thebaine
and oripavine. US 2004/0197428 A1, 2004. (b) Millgate, A. G.;
Pogson, B. J.; Wilson, I. W.; Kutchan, T. M.; Zenk, M. H.; Gerlach, W.
L.; Fist, A. J.; Larkin, P. J. Nature 2004, 431, 413−414.
(23) Waste prevention is one of the most important principals of
green chemistry: Anastas, P. T.; Warner, J. C. In Green Chemistry:
Theory and Practice; University Press: Oxford, 1998.
(8) For studies on the hydrogenation of thebaine, see: Leisch, H.;
Carroll, R. J.; Hudlicky, T.; Cox, D. P. Tetrahedron Lett. 2007, 48,
3979−3981 and references therein..
(9) For one pot procedures to synthesize hydrocodone from thebaine
by hydrogenation in acidic media, see: (a) Carroll, R. J.; Leisch, H.;
Rochon, L.; Hudlicky, T.; Cox, D. P. J. Org. Chem. 2009, 74, 747−752.
(b) Carroll, R. J.; Leisch, H.; Hudlicky, T. Conversion of thebaine to
morphine derivatives. US 7928234B2, 2011.
(24) (a) Imada, Y.; Iida, H.; Ono, S.; Murahashi, S.-I. J. Am. Chem.
Soc. 2003, 125, 2868−2869. (b) Imada, Y.; Iida, H.; Ono, S.; Masui, Y.;
Murahashi, S.-i. Chem. - Asian J. 2006, 1, 136−147. (c) Imada, Y.;
Tonomura, I.; Komiya, N.; Naota, T. Synlett 2013, 24, 1679−1682.
(26) Ebnesajjad, S.; Khaladkar, P. R. In Fluoropolymers Applications in
the Chemical Processing Industries: The Definitive User’s Guide and
Databook; Elsevier Science, 2008.
(27) For a recent review about fouling in microstructured devices,
see: Schoenitz, M.; Grundemann, L.; Augustin, W.; Scholl, S. Chem.
Commun. 2015, 51, 8213−8228.
(28) Haber, J.; Kashid, M. N.; Renken, A.; Kiwi-Minsker, L. Ind. Eng.
Chem. Res. 2012, 51, 1474−1489.
(10) (a) Hunig, S.; Muller, H. R.; Thier, W. Angew. Chem., Int. Ed.
̈
̈
Engl. 1965, 4, 271−280. (b) Pasto, D. J.; Taylor, R. T. Org. React.
1991, 40, 91−155.
(11) (a) Grew, E. L.; Robertson, A. A. Reduction of thebaine. US
3812132, 1974;. (b) Orr, B.; Dummitt, W. E. Methods for producing
hydrocodone, hydromorphone or a derivative thereof. US 8399671B2,
2013.
(29) (a) Barthe, P.; Guermeur, C.; Lobet, O.; Moreno, M.; Woehl,
P.; Roberge, D. M.; Bieler, N.; Zimmermann, B. Chem. Eng. Technol.
2008, 31, 1146−1154. (b) Roberge, D. M.; Bieler, N.; Mathier, M.;
Eyholzer, M.; Zimmermann, B.; Barthe, P.; Guermeur, C.; Lobet, O.;
Moreno, M.; Woehl, P. Chem. Eng. Technol. 2008, 31, 1155−1161.
(12) Eppenberger, U.; Warren, M. E.; Rapoport, H. Helv. Chim. Acta
1968, 51, 381−397.
(13) Feth, M. P.; Rossen, K.; Burgard, A. Org. Process Res. Dev. 2013,
17, 282−293.
I
Org. Process Res. Dev. XXXX, XXX, XXX−XXX