Table of Contents

November 2003
Volume 7, Issue 6
Pages 775-1085

Editorial

Easier-To-Read Reaction Schemes

Trevor Laird
p 775
Publication Date (Web): October 15, 2003 (Editorial)
DOI: 10.1021/op034140f

Highlights from the Literature

Some Items of Interest to Process R&D Chemists and Engineers

Trevor Laird*Stephen A. HermitageUlf Tilstam
pp 776–783
Publication Date (Web): November 01, 2003 (Editorial)
DOI: 10.1021/op034145c

Highlights from the Patents

A Review of U.S. Patents in the Field of Organic Process Development Published during April to July 2003

Keith Turner
pp 784–793
Publication Date (Web): October 11, 2003 (Highlights From Patents)
DOI: 10.1021/op034135b

Articles

A Convenient Nitroxyl Radical Catalyst for the Selective Oxidation of Primary and Secondary Alcohols to Aldehydes and Ketones by O2 and H2O2 under Mild Conditions

Francesco Minisci,*† Francesco Recupero,† Marianna Rodinò,† Massimiliano Sala,‡ and Armin Schneider§
pp 794–798
Publication Date (Web): August 26, 2003 (Article)
DOI: 10.1021/op034063o

A Scalable Synthesis of Meso-Substituted Dipyrromethanes

Joydev K. Laha, Savithri Dhanalekshmi, Masahiko Taniguchi, Arounaguiry Ambroise, and Jonathan S. Lindsey*
pp 799–812
Publication Date (Web): September 09, 2003 (Article)
DOI: 10.1021/op034083q

Phase-Transfer Catalytic Reaction of 4,4‘-Bis(Chloromethyl)-1,1‘-biphenyl and 1-Butanol in a Two-Phase Medium

Maw-Ling Wang*†Ze-Fe Lee
pp 813–820
Publication Date (Web): August 13, 2003 (Article)
DOI: 10.1021/op030002e

Development of Jacobsen Asymmetric Epoxidation and Sharpless Asymmetric Dihydroxylation Methods for the Large-Scale Preparation of a Chiral Dihydrobenzofuran Epoxide

J. Siva Prasad,* Truc Vu, Michael J. Totleben, Gerard A. Crispino, David J. Kacsur, Shankar Swaminathan, John E. Thornton, Alan Fritz, and Ambarish K. Singh
pp 821–827
Publication Date (Web): October 09, 2003 (Article)
DOI: 10.1021/op025622e

Enzymatic Hydrocyanation of a Sterically Hindered Aldehyde. Optimization of a Chemoenzymatic Procedure for (R)-2-Chloromandelic Acid

Luuk M. van Langen, Fred van Rantwijk, and Roger A. Sheldon*
pp 828–831
Publication Date (Web): September 12, 2003 (Article)
DOI: 10.1021/op0340964

Synthesis of High-Quality Antisense Drugs. Addition of Acrylonitrile to Phosphorothioate Oligonucleotides:  Adduct Characterization and Avoidance

Daniel C. Capaldi, Hans Gaus, Achim H. Krotz, Jim Arnold, Ricaldo L. Carty, Max N. Moore, Anthony N. Scozzari, Kirsten Lowery, Douglas L. Cole, and Vasulinga T. Ravikumar*
pp 832–838
Publication Date (Web): September 25, 2003 (Article)
DOI: 10.1021/op020090n

The Chemical Development of LB71350

Kyu Woong Lee, Sang Yeul Hwang, Chung Ryeol Kim, Do Hyun Nam, Jay Hyok Chang, Sang Chul Choi, Bo Seung Choi, Hyeong-wook Choi, Ki Kon Lee, Byungran So, Sung Wook Cho, and Hyunik Shin*
pp 839–845
Publication Date (Web): October 03, 2003 (Article)
DOI: 10.1021/op034062w

Practical Large-Scale Synthesis of Doripenem:  A Novel 1β-Methylcarbapenem Antibiotic

Yutaka Nishino,† Makoto Kobayashi, Taneyoshi Shinno, Kenji Izumi, Hiroshi Yonezawa,‡ Yoshiyuki Masui,* and Masayuki Takahira§
pp 846–850
Publication Date (Web): September 24, 2003 (Article)
DOI: 10.1021/op034088n

An Efficient and Cost-Effective Synthesis of Pagoclone

Timothy L. Stuk,*† Bryce K. Assink,† Ronald C. Bates, Jr.,‡ David T. Erdman,† Victor Fedij,† Sandra M. Jennings,† Jennifer A. Lassig,† Randy J. Smith,‡ and Traci L. Smith†
pp 851–855
Publication Date (Web): September 17, 2003 (Article)
DOI: 10.1021/op034060b

An Expedient Synthesis of LAF389, a Bengamide B Analogue

David D. Xu, Liladhar Waykole,* John V. Calienni, Lech Ciszewski, George T. Lee, Wenming Liu, Joanna Szewczyk, Kevin Vargas, Kapa Prasad, Oljan Repi, and Thomas J. Blacklock
pp 856–865
Publication Date (Web): September 23, 2003 (Article)
DOI: 10.1021/op0341162

A Practical Synthesis of the Platelet Fibrinogen Antagonist, Elarofiban

Judith H. Cohen,* Mary Ellen Bos, Sergio Cesco-Cancian,† Bruce D. Harris,§ John T. Hortenstine,§ Michael Justus,‡ Cynthia A. Maryanoff,§ John Mills,§ Stefan Muller,‡ Armin Roessler,‡ Lorraine Scott,§ Kirk L. Sorgi,† Frank J. Villani, Jr.,§ Robin R. H. Webster,† and Christian Weh‡
pp 866–872
Publication Date (Web): October 01, 2003 (Article)
DOI: 10.1021/op034103o

Synthesis and Purification of 6-Ethoxy-4-oxo-1,4-dihydro-[1,5]naphthyridine-3-carboxylic Acid Benzylamide

Justin Beaudin, Dennis E. Bourassa, Paul Bowles, Michael J. Castaldi, Ronald Clay, Michel A. Couturier, Gregory Karrick, Teresa W. Makowski, Ruth E. McDermott, Clifford N. Meltz, Morgan Meltz, James E. Phillips, John A. Ragan, David H. Brown Ripin,* Robert A. Singer, John L. Tucker, and Lulin Wei
pp 873–878
Publication Date (Web): September 30, 2003 (Article)
DOI: 10.1021/op0341061

Inhibition of the Cobalt Acetate/Bromide-Catalyzed Hydrogen Peroxide Oxidation of 4-tert-Butyltoluene

Ahmed A. Amin and James K. Beattie*
pp 879–882
Publication Date (Web): October 15, 2003 (Article)
DOI: 10.1021/op0340614

Practical Synthesis of N-{4-[(2-Methyl-4,5-dihydroimidazo[4,5-d][1]benzazepin- 6(1H)-yl)carbonyl]phenyl}biphenyl-2-carboxamide Monohydrochloride:  an Arginine Vasopressin Antagonist

Takashi Tsunoda,* Atsuki Yamazaki,† Hidenori Iwamoto,‡ and Shuichi Sakamoto
pp 883–887
Publication Date (Web): November 01, 2003 (Article)
DOI: 10.1021/op034079e

CO2 Offgas as a Mechanistic Probe and Scale-up Tool in N-Acylations Using Mixed Anhydrides from Amino Acids and Isobutyl Chloroformate

Apurva Chaudhary, Michael J. Girgis,* Mahavir Prashad,* Bin Hu, Denis Har, Oljan Repi, and Thomas J. Blacklock
pp 888–895
Publication Date (Web): October 30, 2003 (Article)
DOI: 10.1021/op034085a

Synthesis and Characterisation of Impurities of Manufacture in Support of Certificate of the European Pharmacopoeia Applications Part 1 (Clobetasone Butyrate)

Stephen McGhie,*† Alan Sewell,‡ John Devlin,§ Mark J. Wilson,‡ Lee Newton,‡ Kirsty McLaren,‡ Maranda Thomson,‡ Steven Cobb,‡ Jacqueline Ferguson,‡ and Kevin Prudhoe‡
pp 896–903
Publication Date (Web): November 06, 2003 (Article)
DOI: 10.1021/op0341216

A New Practical Route for the Manufacture of (4aR,10aR)-9-Methoxy-1-methyl-6-trimethylsilanyl- 1,2,3,4,4a,5,10,10a-octahydrobenzo[g]quinoline

Markus Bänziger,*† Ernst Küsters,† Luigi La Vecchia,‡ Wolfgang Marterer,*† and J. Nozulak§
pp 904–912
Publication Date (Web): November 05, 2003 (Article)
DOI: 10.1021/op034112x

Technical Notes

Process Development and Pilot Plant Scale Synthesis of Spiro[3.5]nonane-6,8-dione

Thomas E. Lehmann, Oliver Kuhn, and Jochen Krüger*
pp 913–916
Publication Date (Web): August 26, 2003 (Technical Note)
DOI: 10.1021/op0340560

Efficient Synthesis of Antisense Phosphorothioate Oligonucleotides:  Evaluation of Dichloroacetic Acid at Higher Concentration to Reduce Cycle Time

Zacharia S. Cheruvallath, Recaldo L. Carty, Mark Andrade, Max N. Moore, Quinlai Song, Claus Rentel, Douglas L. Cole, and Vasulinga T. Ravikumar*
pp 917–920
Publication Date (Web): September 25, 2003 (Technical Note)
DOI: 10.1021/op030006j

A Convenient Synthesis of High-Purity 1-Chloro-2,6-difluorobenzene

Robert M. Moore, Jr.*
pp 921–924
Publication Date (Web): September 06, 2003 (Technical Note)
DOI: 10.1021/op0340816

Hydrolysis of Cyclic Phosphites/Phosphoramidites and Its Inhibition-Reversible Cyclization of Acyclic Phosphonate Salts to Cyclic Phosphites

N. Satish Kumar, Sudha Kumaraswamy, Musa A. Said, and K. C. Kumara Swamy*
pp 925–928
Publication Date (Web): September 06, 2003 (Technical Note)
DOI: 10.1021/op034058k

Chemoselective Removal of Dimeric 1,3-Diol Impurities Generated from Methyl Grignard Addition onto Esters

John L. Tucker,* Michel Couturier, Kyle R. Leeman, Matthew P. Hinderaker, and Brian M. Andresen
pp 929–932
Publication Date (Web): October 02, 2003 (Technical Note)
DOI: 10.1021/op025597c

Process for Developing 3β-[4-(S)-Arylacetylamino-4β-(2-(2-furyl)ethyl]azetidin-2-one:  A Carbacephem Key Intermediate

Yatendra Kumar,* Neera Tewari, Hashim Nizar, Bishwa Prakash Rai, and Shailendra Kumar Singh
pp 933–935
Publication Date (Web): October 02, 2003 (Technical Note)
DOI: 10.1021/op034074h

A Kinetic Study of 2-Ethyl-1-hexanol Oxidation by Dichromate Using Clay-Supported 1-Butyl 4-aza-1-azonia Bicyclo[2.2.2]octane Chloride as the Phase-Transfer Catalyst

M. Ghiaci,* R. J. Kalbasi, and M. E. Sedaghat
pp 936–938
Publication Date (Web): October 23, 2003 (Technical Note)
DOI: 10.1021/op034120d

Synthesis of T2288:  From Bench Synthesis to Pilot Production

Michel Guillaume,* Jef Cuypers, Ivan Vervest, Dirk De Smaele, and Stef Leurs
pp 939–941
Publication Date (Web): October 24, 2003 (Technical Note)
DOI: 10.1021/op034117u

Technology Reports

Modelling the Kinetics of a Reaction Involving a Sodium Salt of 1,2,4-Triazole and a Complex Substituted Aliphatic Halide

H. Grénman,† T. Salmi,*† P. Mäki-Arvela,† J. Wärnå,† K. Eränen,† E. Tirronen,‡ and A. Pehkonen§
pp 942–950
Publication Date (Web): September 20, 2003 (Technology Report)
DOI: 10.1021/op0300138

Pilot-Scale Lipase-Catalyzed Regioselective Acylation of Ribavirin in Anhydrous Media in the Synthesis of a Novel Prodrug Intermediate

Maria Tamarez, Brian Morgan,† George S. K. Wong, Weidong Tong, Frank Bennett, Raymond Lovey, Jinping L. McCormick, and Aleksey Zaks*
pp 951–953
Publication Date (Web): December 18, 2002 (Technology Report)
DOI: 10.1021/op0255938

A Comparison between Kinetic Parameters from the Synthesis of Tris(p-nitrophenyl)phosphite and Tris(p-nitrophenyl)phosphate Using Reaction Calorimetry

Rafael C. Seiceira, Carlos F. P. Machado e Silva, Luciana R. M. Estevão, and João F. Cajaiba da Silva*
pp 954–956
Publication Date (Web): October 09, 2003 (Technology Report)
DOI: 10.1021/op034100b

Special Feature Section: Polymorphism and Crystallization

SPECIAL FEATURE SECTION:  POLYMORPHISM AND CRYSTALLIZATION

Trevor Laird
p 957
Publication Date (Web): October 09, 2003 (Editorial)
DOI: 10.1021/op034139g

An Etoricoxib Phase Diagram:  Hemihydrate and Anhydrate

Louis S. Crocker,* Zhihong Ge, Ahmed Abrahim, Robert Hartman, and Jing Xu
pp 958–961
Publication Date (Web): July 16, 2003 (Technology Report)
DOI: 10.1021/op025612d

Polymorphic Study of l-Arginine Salt of Ragaglitazar (DRF-2725)†

S. Raju,‡ P. Rajender Kumar,‡ K. Vyas,§ D. Srinivas Rao,§ M. R. Sarma,‡ S. Vishnuvardhan Reddy,§ M. Nirmala,§ and G. Om Reddy*‡
pp 962–969
Publication Date (Web): October 31, 2003 (Article)
DOI: 10.1021/op030025t

Structural Characterization of Industrially Relevant Polymorphic Materials from Powder Diffraction Data

Kenneth D. M. Harris* and Eugene Y. Cheung
pp 970–976
Publication Date (Web): November 01, 2003 (Summary of Lecture Transcript)
DOI: 10.1021/op030036m

In Situ Monitoring of Polymorphic Transitions

Brian O'Sullivan,† Paul Barrett,‡ Gregor Hsiao,‡ Alun Carr,§ and Brian Glennon*†
pp 977–982
Publication Date (Web): November 06, 2003 (Technology Report)
DOI: 10.1021/op030031p

Phase Transitions in Supersaturated Drug Solution

Stéphane Veesler,*‡ Laurent Lafferrère,‡ Eric Garcia,§ and Christian Hoff
pp 983–989
Publication Date (Web): November 21, 2003 (Article)
DOI: 10.1021/op034089f

Salt Selection and Simultaneous Polymorphism Assessment via High-Throughput Crystallization:  The Case of Sertraline

Julius F. Remenar,* J. Michael MacPhee, Bridget K. Larson, Viraj A. Tyagi, Jason H. Ho, David A. McIlroy, Magali B. Hickey, Paul B. Shaw, and Örn Almarsson
pp 990–996
Publication Date (Web): October 14, 2003 (Article)
DOI: 10.1021/op034115+

Crystallization Process Development of an Active Pharmaceutical Ingredient and Particle Engineering via the Use of Ultrasonics and Temperature Cycling

Soojin Kim,* Chenkou Wei, and San Kiang
pp 997–1001
Publication Date (Web): November 01, 2003 (Article)
DOI: 10.1021/op034107t

Particle Engineering Using Power Ultrasound1

Robert Daniel Dennehy*
pp 1002–1006
Publication Date (Web): October 25, 2003 (Summary of Lecture Transcript)
DOI: 10.1021/op034124i

Combined Effect of Polymorphism and Process on Preferential Crystallization:  Example with (±)-5(4‘-Methylphenyl)-5-methylhydantoin

L. Courvoisier, L. Mignot, M. N. Petit, and G. Coquerel*
pp 1007–1016
Publication Date (Web): November 21, 2003 (Article)
DOI: 10.1021/op030022g

Structural and Thermodynamic Explanations of Ostwald's Rule

Terry Threlfall
pp 1017–1027
Publication Date (Web): November 21, 2003 (Article)
DOI: 10.1021/op030026l

Special Feature Section: Safety of Chemical Processes

SPECIAL FEATURE SECTION: SAFETY OF CHEMICAL PROCESSES

Trevor Laird
p 1028
Publication Date (Web): October 11, 2003 (Article)
DOI: 10.1021/op034138o

Safety Notables:  Information from the Literature

David J. am EndePaul F. Vogt
pp 1029–1033
Publication Date (Web): October 23, 2003 (Editorial)
DOI: 10.1021/op034143s

Rapid Scale-Up of the Matrix Metalloproteinase Inhibitor CH5902:  Process Safety and Route Development Considerations

Ian H. Smith,* Anthony Alorati,† Graham Frampton, Steve Jones, John O'Rourke, and Martin W. Woods‡
pp 1034–1039
Publication Date (Web): August 30, 2003 (Article)
DOI: 10.1021/op0340762

Safety Aspects of the Under-Pressure Reaction of Trichloroacetyl Chloride and Acrylonitrile in the Preparation of 3,5,6-Trichloro-2-pyridinol

H. Fakhraian,* A. Bazaz, and H. Hadj-Ghanbary
pp 1040–1042
Publication Date (Web): July 19, 2003 (Technical Note)
DOI: 10.1021/op0340558

Safety vs Efficiency in the Development of a High-Energy Compound

Sally Gut Ruggeri,* David R. Bill, Dennis E. Bourassa, Michael J. Castaldi, Tim L. Houck, David H. Brown Ripin, Lulin Wei, and Neil Weston†
pp 1043–1047
Publication Date (Web): October 01, 2003 (Article)
DOI: 10.1021/op0341059

Electrostatic Hazards in Liquids and Relevance to Process Chemistry

Matthew R. Giles*
pp 1048–1050
Publication Date (Web): October 23, 2003 (Safety/Environmental Report)
DOI: 10.1021/op0340863

Improvement of the Experimental Testing Method for the Determination of the Influence of Air on the Thermal Stability of Chemical Compounds

Jacques Wiss*† and Jean Fuchs‡
pp 1051–1058
Publication Date (Web): August 21, 2003 (Technical Note)
DOI: 10.1021/op034050a

Online Spectroscopic Investigations (FTIR/Raman) of Industrial Reactions:  Synthesis of Tributyltin Azide and Hydrogenation of Chloronitrobenzene

Jacques Wiss*† and Arne Zilian‡
pp 1059–1066
Publication Date (Web): June 17, 2003 (Technology Report)
DOI: 10.1021/op030009w

Reaction Safety:  An Improved Procedure for the Preparation of 1,3,4,12a-Tetrahydro-11H-[1,4]-oxanio[3,4-c][1,4]benzodiazepine-6,12-dione with Iron in Acetic Acid

Jeffrey Grimm, Fuqiang Liu, Stephen Stefanick,* Kirk L. Sorgi, and Cynthia A. Maryanoff
pp 1067–1070
Publication Date (Web): August 09, 2003 (Safety/Environmental Report)
DOI: 10.1021/op034073p

Evaluation and Optimisation of the Reagent Addition Sequence during the Synthesis of Atrazine (6-Chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) Using Reaction Calorimetry

Benita Barton, Shawn Gouws, Melissa C. Schaefer, and Bernard Zeelie*
pp 1071–1076
Publication Date (Web): October 11, 2003 (Article)
DOI: 10.1021/op0340715

A New Multipurpose Microreactor for Process Safety Studies

L. Bou-Diab, H. Fierz, C. Gwerder, and G. Suter*
pp 1077–1078
Publication Date (Web): October 24, 2003 (Technical Note)
DOI: 10.1021/op030030x

Calorimetric Approach and Simulation for Scale-Up of a Friedel−Crafts Reaction

Lucia Gigante, Angelo Lunghi, Simone Martinelli, and Paolo Cardillo*Luca Picello, Roberto Bortolaso, and Marco GalvagniRenato Rota
pp 1079–1082
Publication Date (Web): November 06, 2003 (Technology Report)
DOI: 10.1021/op030043a

Additions & Corrections

Evaluation of Kinetic Parameters from the Synthesis of Triaryl Phosphates Using Reaction Calorimetry

Carlos F. Pinto Machado e Silva, and Joao F. Cajaiba da Silva
p 1083
Publication Date (Web): October 09, 2003 (Addition/Correction)
DOI: 10.1021/op0300387

Some Items of Interest to Process R&D Chemists and Engineers

Trevor Laird*, Stephen A. Hermitage, and Ulf Tilstam
p 1083
Publication Date (Web): October 09, 2003 (Addition/Correction)
DOI: 10.1021/op0341418

Book Reviews