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(19) TZZ_Z¥_T (11) EP 1 907 355 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07C 303/22 (2006.01) C07C 303/38 (2006.01) 05.08.2015 Bulletin 2015/32 C07D 209/22 (2006.01) C07D 209/18 (2006.01) (21) Application number: 06800157.7 (86) International application number: PCT/US2006/028182 (22) Date of filing: 20.07.2006 (87) International publication number: WO 2007/013974 (01.02.2007 Gazette 2007/05) (54) PROCESS FOR THE SYNTHESIS OF SULFONYL HALIDES AND SULFONAMIDES FROM SULFONIC ACID SALTS VERFAHREN FÜR DIE SYNTHESE VON SULFONYLHALIDEN UND SULFONAMIDEN AUS SULFONSÄURESALZEN PROCÉDÉ DE SYNTHÈSE D’HALOGÉNURES DE SULFONYLE ET DE SULFONAMIDES À PARTIR DE SELS D’ACIDE SULPHONIQUE (84) Designated Contracting States: • D. BRUNDISH ET AL.: "Design and Synthesis of AT BE BG CH CY CZ DE DK EE ES FI FR GB GR Thrombin Inhibitors: Analogues of MD-805 with HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI Reduced Stereogenicity and Improved Potency" SK TR J. MED. CHEM., vol. 42, no. 22, 1999, pages 4584-4603, XP002414353 (30) Priority: 21.07.2005 US 701158 P • R. A. ABRAMOVITCH ET AL.: "Solution and Flash Vacuum Pyrolysis of Some 2,6- (43) Date of publication of application: Disubstituted .beta.-Phenethylsulfonyl Azides 09.04.2008 Bulletin 2008/15 and of .beta.-Styrenesulfonyl Azide" J. ORG. CHEM., vol. 50, no. 12, 1985, pages 2066-2073, (73) Proprietor: Ziarco Pharma Ltd XP002414354 Canterbury • "Houben-Weyl: Methoden der Organischen Kent CT1 2NF (GB) Chemie, 4. ed." 1955, GEORG THIEME VERLAG , STUTTGART DE , XP002414355 page 563, last (72) Inventors: paragraph, first two lines • MICHALAK, Ronal, Stanley • DATABASE BEILSTEIN BEILSTEIN INSTITUTE Congers, NY 10920 (US) FORORGANIC CHEMISTRY, FRANKFURT- MAIN, • HELOM, Jean Louise DE; XP002414363 Database accession no. BRN Hillsdale, NJ 07642 (US) 5427164 & J. ZINCZUK ET AL.: J. HETEROCYCL. • ZELDIS, Joseph CHEM., vol. 29, no. 4, 1992, pages 859-866, New City, NY 10956 (US) • DATABASE BEILSTEIN BEILSTEIN INSTITUTE FORORGANIC CHEMISTRY, FRANKFURT- MAIN, (74) Representative: Rutt, Jason Edward et al DE; XP002414364 Database accession no. BRN Rouse IP Limited 2717732 & R. EGLI; C.H. EUGSTER: HEL. CHIM. 11th Floor, Exchange Tower ACTA, 58, 1975, pages 2321-2346, 1 Harbour Exchange Square • DATABASE BEILSTEIN BEILSTEIN INSTITUTE London E14 9GE (GB) FORORGANIC CHEMISTRY, FRANKFURT- MAIN, DE; XP002414365 Database accession no. BRN (56) References cited: 1747453 & FRANCHIMONT; KLOBBIE: RECL. WO-A2-03/048122 US-A- 2 507 408 TRAV. CHIM. PAYS-BAS, 5, 1886, page 277, US-A- 2 888 486 Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 1 907 355 B1 Printed by Jouve, 75001 PARIS (FR) (Cont. next page) EP 1 907 355 B1 • DATABASE BEILSTEIN BEILSTEIN INSTITUTE • DATABASE BEILSTEIN BEILSTEIN INSTITUTE FORORGANIC CHEMISTRY, FRANKFURT- MAIN, FORORGANIC CHEMISTRY, FRANKFURT- MAIN, DE; XP002414366 Database accession no. BRN DE; XP002414369 Database accession no. BRN 2697078 & H. L. YALE; J. T. SHEEHAN: J.ORG. 2639938 & V. BRAUN ET AL.: CHEM. BER. 63, CHEM., vol. 26, 1961, pages 4315-4325, 1930, page 2847, 2861, • DATABASE BEILSTEIN BEILSTEIN INSTITUTE FORORGANIC CHEMISTRY, FRANKFURT- MAIN, DE; XP002414367 Database accession no. BRN 2703228, 2702138 & FEIT: ACTA CHEM. SCAN., 16, 1962, page 275, 277, • DATABASE BEILSTEIN BEILSTEIN INSTITUTE FORORGANIC CHEMISTRY, FRANKFURT- MAIN, DE; XP002414368 Database accession no. BRN 3255360 & TRUCE, MILIONIS: J. AM. CHEM. SOC., vol. 74, 1952, page 974, 975, 2 EP 1 907 355 B1 Description [0001] This application claims benefit of priority to US provisional patent application serial no. 60/701,158 filed on July 21, 2005. 5 FIELD OF THE INVENTION [0002] The present invention relates to processes for the preparation of sulfonyl halides and sulfonamides useful as intermediates in the preparation of, for example, pharmaceuticals and for the preparation of sulfonamides useful as 10 pharmaceuticals. BACKGROUND OF THE INVENTION [0003] Sulfonyl chlorides are widely used in the chemical industry such as for the preparation of dyes, lithographic 15 resists, and pharmaceuticals. They can be further transformed into other functional groups such as aromatic sulfones (by Friedel-Crafts sulfonylation of aromatic substrates) or sulfonamides (by reaction with amines) (see, e.g., Kirk-Othmer Encyclopedia of Chemical Technology). Sulfonamides are integral functional groups of a wide variety of therapeutic small molecule drugs such as antibacterial agents, diuretics, and cPLA 2 inhibitors. [0004] A typical preparation of sulfonyl chlorides involves reaction of the sodium salt of a sulfonic acid with phosphorus 20 pentachloride, sometimes in combination with phosphorus oxychloride or thionyl chloride, frequently with heating of the reaction mixture (see, e.g., March, Advanced Organic Chemistry, 4th ed., John Wiley & Sons, 1992, p.499). These relatively harsh reaction conditions are unsuitable for the preparation of sterically hindered sulfonyl chlorides, such as arylalkylsulfonyl chlorides and the like, which can result in low yields due to the elimination of sulfur dioxide (Nakayama et al., Tet Lett., 1984, 25, 4553-4556). A milder, infrequently used method for the synthesis of sulfonyl chlorides is the 25 reaction of tetrabutylammonium salts of sulfonic acids with triphenylphosphine/sulfuryl chloride (Widlanski et al., Tet. Lett., 1992, 33, 2657-2660), a method that suffers from the disadvantage of poor atom efficiency. [0005] Numerous sterically hindered sulfonyl halides such as (2-trifluoromethylphenyl)-methanesulfonyl chloride and other aryl- and heteroaryl-alkylsulfonyl halides are specifically useful in the preparation of cPLA2 inhibitors for the treat- ment of asthma or arthritic and rheumatic disorders as described in, for example, WO 2003/048122. As discussed above, 30 these intermediates can be difficult to prepare due to loss of sulfur dioxide at higher temperatures and formation of significant amounts of impurities. Thus, new and improved methods for making these compounds, and the corresponding sulfonamides, are needed. The methods provided herein help meet these and other needs. SUMMARY OF THE INVENTION 35 [0006] In some embodiments, the present invention provides a synthetic process comprising reacting a compound of Formula II: -1 [Ar-(R)z-SO3 ]qM II 40 wherein: Ar is phenyl substituted with one perhaloalkyl group at the 2 position thereof; R is methylene; 45 M is a Group I or II metal ion; q is 1 where M is Group I metal ion; or q is 2 where M is a Group II metal ion; and 50 z is 1 ; with a halogen substitution reagent in the presence of a catalytic amount of water and in the presence of a co-catalyst for a time and under conditions sufficient to form a compound of Formula III: 55 Ar-(R)2-SO2-X III wherein X is halogen. 3 EP 1 907 355 B1 [0007] In some embodiments, the synthetic processes of the present invention further include reacting the compound of Formula III with an amine reagent, optionally in the presence of a base, for a time and under conditions sufficient to form a compound of Formula I: 5 4 5 Ar-(R)2-SO2-NR R I wherein: 4 5 R and R are each, independently, H, C1-C18 alkyl, C2-C18 alkenyl, C2-C18 alkynyl, C3-C18 cycloalkyl, heterocy- 10 cloalkyl, aryl or heteroaryl, each optionally substituted by up to five substituents independently selected from the group consisting of halogen, C 1-C6 alkyl, C 3-C7 cycloalkyl, heterocycloalkyl, cyano, nitro, OH, C 1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloaikoxy, aryl and heteroaryl; or R4 and R5 together with the N atom to which they are attached can form a 5- or 6-membered heterocycle. 15 DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION [0008] Described is a process for the preparation of sulfonyl halides and sulfonamides, such as aryl- and heteroaryl- alkylsulfonyl halides and aryl- and heteroaryl-alkylsulfonamides, including (2-trifluoromethylphenyl)- methanesulfonyl 20 chloride and (2-trifluoromethylphenyl)-methanesulfonamide, which are intermediates in the synthesis of certain CPLA2 inhibitors. In some embodiments, the processes involve the formation of the intermediate sulfonic acid prior to conversion to the sulfonyl halide. [0009] Described is a synthetic process that includes reacting a compound of Formula II: 25 -1 [Ar-(R)2-SO3 ]qM II wherein: Ar is C1-C18 alkyl, C2-C18 alkenyl, C2-C18 alkynyl, C3-C18 cycloalkyl, heterocycloalkyl, aryl or heteroaryl, each 30 optionally substituted by up to five substituents independently selected from the group consisting of halogen, C 1-C6 alkyl, C3-C7 cycloalkyl, heterocycloalkyl, cyano, nitro, OH, C 1-C6 haloalkyl, C 1-C3 perhaloalkyl, C 1-C6 alkoxy, C 1-C6 1 2 1 3 3 3 3 haloalkoxy, C1-C3 perhaloalkoxy, NR R , NR COR , COR , COOR , OCOR , aryloxy, heteroaryloxy, arylalkyloxy, heteroarylalkyloxy, cycloalkylalkyl, arylalkyl, heteroarylalkyl, aryl and heteroaryl; R is C1-C6 alkylenyl; 35 1 2 each R and R is independently selected from the group consisting of H, C 1-C6 alkyl and C3-C7 cycloalkyl; or any R1 and R2, together with the nitrogen atom to which they are attached, can form a 5- or 6- membered heterocycle; 3 each R is independently selected from the group consisting of H, C 1-C6 alkyl and C3-C7 cycloalkyl; M is a Group I or II metal ion; 40 q is 1 where M is Group I metal ion; or q is 2 where M is a Group II metal ion; and z is 0 or 1; with a halogen substitution reagent in the presence of a catalytic amount of water and in the presence of a co-catalyst 45 for a time and under conditions sufficient to form a compound of Formula III: Ar-(R)z-SO2-X III wherein X is halogen.
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  • Process for Polymerizing Acrylonitrile

    Process for Polymerizing Acrylonitrile

    HH HI H HH I H HI H HI H HI II HI H HI II HI II HI H HI II HI HI H H HI I HI European Patent Office Office europeen des brevets EP 0 872 493 A2 EUROPEAN PATENT APPLICATION (43) Date of publication: (51) |nt CI.6: C08F 20/44 21.10.1998 Bulletin 1998/43 (21) Application number: 98302755.8 (22) Date of filing: 08.04.1998 (84) Designated Contracting States: (72) Inventor: Percec, Virgil AT BE CH CY DE DK ES Fl FR GB GR IE IT LI LU Chagrin Falls, Ohio 44022 (US) MC NL PT SE Designated Extension States: (74) Representative: Hoey, Shona AL LT LV MK RO SI BP International Limited Patents and Agreements Division (30) Priority: 14.04.1997 US 843259 Chertsey Road Sunbury-on-Thames, Middlesex TW16 7LN (GB) (71) Applicant: Case Western Reserve University Cleveland, Ohio 44106 (US) (54) Process for polymerizing acrylonitrile (57) This invention relates to a process for polymer- substituted halopropionitriles in the form of monoad- ising acrylonitrile, comprising: (A) forming a polymeris- ducts derived from sulfonyl halides and acrylonitrile, or able mixture comprising acrylonitrile monomer, solvent monoadducts derived from substituted sulfonyl halides and a metal catalyst; (B) contacting said mixture with an and monomers other than acrylonitrile; and (C) polymer- initiator, said initiator being selected from the group con- ising said acrylonitrile monomer to form a polymer com- sisting of sulfonyl halides, halopropionitriles, substituted prised of acrylonitrile. In one embodiment, the polymer- halopropionitriles in the form of monoadducts derived isable mixture in step (A) further comprises at least one from sulfonyl halides and acrylonitrile, monoadducts de- polymerisable comonomer other than acrylonitrile, and rived from substituted sulfonyl halides and monomers the polymer formed during step (C) is a copolymer or a other than acrylonitrile; or polymers containing end multicomponent copolymer comprised of acrylonitrile groups derived from sulfonyl halides, halopropionitriles, and said at least one other polymerisable comonomer.
  • Which Diuretics Are Safe and Effective for Patients with a Sulfa Allergy?

    Which Diuretics Are Safe and Effective for Patients with a Sulfa Allergy?

    From the CLINIcAL InQUiRiES Family Physicians Inquiries Network Ron Healy, MD University of Washington, Which diuretics are safe Seattle; Alaska Family Medicine Residency, Anchorage and effective for patients Terry Ann Jankowski, MLS University of Washington, Seattle with a sulfa allergy? Evidence-based answer Diuretics that do not contain a sulfonamide subsequent allergic reactions to commonly group (eg, amiloride hydrochloride, used sulfonamide-containing diuretics eplerenone, ethacrynic acid, spironolactone, (eg, carbonic anhydrase inhibitors, loop and triamterene) are safe for patients with an diuretics, and thiazides) (strength of allergy to sulfa. The evidence is contradictory recommendation: C, based on case series ® as to whether a history Dowdenof allergy to Healthand poor Media quality case-control and cohort sulfonamide antibiotics increases the risk of studies). Copyright Clinical commentaryFor personal use only Are all sulfa drugs created equal? agents and off-patent, with no company Historical bromides commonly fall by the to take up their cause, no one has been FAST TRACK wayside as better evidence becomes willing to challenge outdated package Reasonable available. Who would have thought 15 insert warnings. years ago that we would be promoting As clinicians who regularly work evidence supports beta-blockers for patients with congestive without a net, we are accustomed to what many of us heart failure? prescribing medications in less than ideal are doing: Using Likewise, with closer inspection, we circumstances. Thankfully, reasonable cheap thiazides have learned that not all sulfa drugs are evidence is available to support what many created equal. The stereospecificity due of us are already doing—using cheap for patients to the absence of aromatic amines in thiazides for patients despite a history of with a history common diuretics means they are safe sulfa allergy.
  • Polyfluoroarenesulfonyl Chlorides Are Usually Obtained by Reactions Of

    Polyfluoroarenesulfonyl Chlorides Are Usually Obtained by Reactions Of

    1 TRANSFORMATIONS OF POLYFLUOROARENESULFONYL HALIDES WITH ALKENES, POLYFLUOROARENETHIOLS AND ALKALI METAL HALIDES * Roman A. Bredikhin , Alexander M. Maksimov and Vyacheslav E. Platonov N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry of the Siberian Branch of Russian Academy of Sciences 630090, Academician Lavrentev Ave., 9, Novosibirsk, Russian Federation E-mail: [email protected] Abstract: The reactions of polyfluoroarenesulfonyl chlorides or bromides with polyfluoroarenethiols gave mixtures of polyfluorinated diaryl disulfides, whereas replacement of fluorine atom at the 4-position of aromatic ring of C6F5SO2F occured. The reactions of polyfluoroarenesulfonyl chlorides or bromides with some n-nucleophiles such as alkali metal halides probably proceed with electron transfer. The reactions of polyfluoroarenesulfonyl bromides with alkenes such as hexene-1 or allyl chloride provided the corresponding adducts in high yields, while the conversion of polyfluoroarenesulfonyl chlorides at the same conditions was poor and C6F5SO2F was unreactive. The reaction of polyfluoroarenesulfonyl bromides with allyl bromide resulted in allyl polyfluoroaryl sulfones. The formation of the products in reactions of polyfluoroareneslfonyl bromdes with alkenes apparently occurs with participation of polyfluoroarenesulfonyl radicals. Keywords: polyfluoroaromatic compounds, sulfonyl bromide, sulfonyl chloride, alkenes, radical addition, allyl polyfluoroaryl sulfone, thiols, metal halides, electron transfer, diaryl disulfide INTRODUCTION Non-fluorinated