US009920002B2de NAR MAN (12 ) United States Patent (10 ) Patent No. : US 9 , 920 ,002 B2 Pleschke et al. (45 ) Date of Patent: Mar . 20 , 2018 ( 54 ) METHODS FOR PRODUCING SULFONIC 8 , 232, 421 B2 7 /2012 Hamprecht et al . ACID DIAMIDES 8 , 541 , 611 B2 9 /2013 Hamprecht et al . 2005/ 0159622 A1 7 /2005 Hamprecht et al . (75 ) Inventors : Axel Pleschke, Mannheim (DE ) ; 2006 /0004220 A1 1 /2006 Hamprecht et al. Thomas Schmidt, Neustadt ( DE ) ; 2008 /0033174 A1 2 /2008 Lohr et al. Joachim Gebhardt, Wachenheim (DE ) ; 2010 /0228054 AL 9 /2010 Keil et al . Sandra Loehr , Ludwigshafen (DE ) ; 2012/ 0310010 Al 12 / 2012 Schmidt et al. Michael Keil, Freinsheim (DE ) ; Jan FOREIGN PATENT DOCUMENTS Hendrik Wevers , Hohen - Suelzen (DE ) DE 1240853 5 / 1967 ( 73 ) Assignee : BASF SE , Ludwigshafen (DE ) EP 1 516 870 3 /2005 JP 50 - 30821 3 / 1975 ( * ) Notice : Subject to any disclaimer, the term of this ( Continued ) patent is extended or adjusted under 35 U . S . C . 154 ( b ) by 184 days . OTHER PUBLICATIONS (21 ) Appl. No. : 12/ 681, 843 Vandi et al . J. Org . Chem . , vol. 26 , No. 4 , ( 1961) , pp . 1136 -1138 .* (22 ) PCT Filed : Oct. 10 , 2008 ( Continued ) ( 86 ) PCT No. : PCT/ EP2008 / 063630 Primary Examiner — Venkataraman Balasubramanian § 371 ( C ) ( 1 ) , ( 74) Attorney , Agent, or Firm — Brinks Gilson & Lione ( 2 ) , ( 4 ) Date : Apr. 6 , 2010 (87 ) PCT Pub. No. : W02009 /050120 (57 ) ABSTRACT PCT Pub . Date : Apr. 23, 2009 The present invention relates to a process for preparing (65 ) Prior Publication Data sulfuric diamides of the general formula I US 2010 /0222586 A1 Sep . 2 , 2010 R 'R ? N — S (O ) 2 - NH2 ( 1) (30 ) Foreign Application Priority Data in which R and R2 are each independently a primary alkyl radical having from 1 to 8 carbon atoms, a secondary alkyl Oct. 12, 2007 (EP ) .. 07118416 radical having from 3 to 8 carbon atoms or a cycloalkyl (51 ) Int. Ci. radical having from 5 to 8 carbon atoms, or , together with C07C 303 /34 ( 2006 . 01 ) the nitrogen atom , form a 5 - to 8 -membered , saturated C07C 307 / 06 ( 2006 .01 ) nitrogen heterocycle which , as well as the nitrogen atom , CO7D 239 /54 ( 2006 .01 ) may have a further heteroatom selected from O and S as a AOIN 43 /54 (2006 .01 ) ring member , where the nitrogen heterocycle is unsubsti C07C 381 /00 ( 2006 . 01) tuted or may have 1 , 2 , 3 or 4 alkyl groups having in each (52 ) U .S . CI. case from 1 to 4 carbon atoms as substituents . The process CPC .. .. .. .. C07C 303 / 34 ( 2013 .01 ) ; A01N 43 /54 comprises the following steps: ( 2013 .01 ) ; C07C 307/ 06 ( 2013 .01 ) ; C07C i ) the reaction of a secondary amine of the formula II 381 /00 (2013 . 01 ) ; C07D 239 /54 ( 2013 .01 ) (58 ) Field of Classification Search R 'R2NH ( II) CPC . .. C07C 303 / 34 ; C07C 307 /06 ; C07D 239 / 54 USPC . .. .. 564 /80 , 84 , 90 , 95 , 79 ; 544 /309 in which R and R ? are each as defined above with sulfuryl See application file for complete search history . chloride in an inert solvent , especially an aromatic sol vent, in the presence of a tertiary amine to give a (56 ) References Cited sulfamoyl chloride of the formula III U . S . PATENT DOCUMENTS R 'RN _ S ( O ) , Cl (III ) 3 , 198 , 785 A 8 / 1965 Houlihan 3 , 709 ,677 A * 1 / 1973 Houlihan 504 / 248 in which R and R2 are each as defined above , and 3 , 962, 326 A 6 / 1976 Semler et al. ii ) reaction of the sulfamoyl chloride of the formula III 4 ,308 ,216 A 12 / 1981 Freitag et al . 4 , 382 , 898 A 5 / 1983 Rudolph et al. obtained in step i ) with ammonia , 5 , 017 ,211 A 5 / 1991 Wenger et al . the sulfamoyl chloride of the formula III being used in step 5 , 238 , 908 A 8 / 1993 Lange et al. ii ) in the form of the solution obtained in step i ) in the inert 5 ,420 , 099 A 5 / 1995 Newton 6 ,251 , 829 B1 6 / 2001 Li et al. solvent, especially the aromatic solvent. 7 , 820 , 846 B2 10 / 2010 Hamprecht et al . 7 , 847 , 097 B2 * 12 / 2010 Gebhardt et al . .. .. .. 544 / 309 8 , 124 ,818 B2 * 2 / 2012 Loehr et al. .. .. 585 / 19 9 Claims, No Drawings US 9 ,920 , 002 B2 Page 2 References Cited Medicinal Chemistry Letters , vol. 16 , No . 4 , (2006 ) , pp . 978 - 983 . (56 ) XP002474074 Audrieth et al. , “ Hydrazides of Sulfuric Acid and Their Derivatives. FOREIGN PATENT DOCUMENTS II. The Sulfamyl Hydrazides , " J . Org . Chem ., vol. 21 , No . 4 , ( 1956 ) , 56 - 30945 3 / 1981 pp . 426 -428 . XP002474073 . 57 - 99553 6 / 1982 Beckert et al. , “ Elecktrophile Aromatische Substitution ,” 61 - 155350 7 / 1986 Organikum , 22nd ed . , (2004 ), pp . 358 - 361. 5 - 279210 10 / 1993 Beckert et al. , “ Reaktionen von Carbonylverbindungen ," = 2001 / 523222 11 / 2001 Organikum , 22nd ed . , (2004 ) , pp . 496 -499 . 2003 - 519130 6 / 2003 Behrend , “ Über die Einwirkung von Sulfurylchlorid auf secundäre 2004 - 501084 1 /2004 Aminbasen , " Justus Liebigs Annalen Der Chemie , vol . 222 , ( 1884 ) , 2004 - 535446 11/ 2004 pp . 116 - 136 . XP002474075 . 2005 - 501827 1 / 2005 Binkley ed Degering, “ Organic Synthesis with Sulfuryl Chloride, ” 2005 - 97138 4 / 2005 J . Am . Chem . Soc ., vol. 61 , ( 1939 ) , pp . 3250 -3251 . XP002474072 . 2006 - 83133 3 / 2006 Hamprecht et al. , “ Alkylsulfanmidsäurechloride als Schlüs WO WO 1989 /002891 4 / 1989 WO WO 98 / 32748 4 / 1998 selbausteine für Neue Pflanzenschutzwirkstoffe ,” Agnew . Chem . , WO WO 01/ 47897 7 / 2001 vol. 93 , ( 1981 ) , pp . 151 - 163 . WO WO 01/ 79203 10 / 2001 International Preliminary Report on Patentability, issued in PCT/ WO WO 2001 /083459 11 / 2001 EP2008 /063630 , dated May 11 , 2010 . WO WO 03 / 002542 1 / 2003 International Search Report , issued in PCT/ EP2008 /063630 , dated WO WO 03 / 007945 1 / 2003 Jan . 30 , 2009 . WO WO 2003 /097589 11 /2003 Scherer et al. , “ Reaktionen mit Benzotrichlorid und wo WO 2004 /035545 4 / 2004 Pentachloräthyl - Benzol, ” Justus Liebigs Annalen der Chemie , vol . WO WO 2004 /039768 5 / 2004 677 , ( 1964 ) , pp . 83 - 95 . WO WO 2004 / 106324 12 / 2004 Unterhalt , “ Schwefesäure -di - N -Derivative , ” in Methoden der WO WO 2006 /010474 2 / 2006 Organischen Chemie [Methods of Organic Chemistry ) , Houben WO WOWY 2006 /090210 8 /2006 Weyl ed ., E11 , ( 1985 ) , pp . 1019 - 1025 . WO WO 2007063028 6 / 2007 Vandi et al. , " Synthesis and Properties of Some N -Substituted Sulfamides, " J . Org . Chem ., vol . 26 , No . 4 , ( 1961 ) , pp . 1136 - 1138 . OTHER PUBLICATIONS XP002474071 . Wheeler et al ., “ Preparation and Properties of Certain Derivatives of Wheeler et al . J . Am . Chem . Soc ., vol. 66 , ( 1944 ) , pp . 1242 - 1243. * Sulfamide, ” J . Am . Chem . Soc ., vol . 66 , ( 1944 ) , pp . 1242 - 1243 . Adkison et al. , " Semicarbazone - Based Inhibitors of Cathepsin K , Are They Prodrugs for Aldehyde Inhibitors ," Bioorganic and * cited by examiner US 9 , 920 , 002 B2 METHODS FOR PRODUCING SULFONIC these compounds in good yields and which can be carried ACID DIAMIDES out with inexpensive starting materials . This object is sur prisingly achieved by the process defined hereinafter. This application is a National Stage application of Inter - The present invention provides a process for preparing national Application No. PCT/ EP2008 / 063630 filed Oct . 10 , 5 sulfuric diamides of the general formula I designated above , 2008 , the entire contents of which is hereby incorporated comprising the following steps: herein by reference . This application also claims the benefit i) the reaction of a secondary amine of the formula II under 35 U . S . C . $ 119 of European Patent Application No. 07118416 . 2 , filed Oct . 12 , 2007 , the entire contents of which R ' R ?NH ( II) is hereby incorporated herein by reference . 10 The present invention relates to a process for preparing in which R and R are each as defined above with sulfuryl chloride in an inert solvent, especially an aromatic sol sulfuric diamides of the general formula I vent, in the presence of a tertiary amine to give a R ' R ? N — S (0 )2 — NH ( 1) sulfamoyl chloride of the formula III in which R and R2 are each independently a primary alkyl 15 radical having from 1 to 8 carbon atoms, a secondary alkyl R ' R ? N — S (0 ) 2 - C1 (III ) radical having from 3 to 8 carbon atoms or a cycloalkyl in which R1 and R2 are each as defined above , and radical having from 5 to 8 carbon atoms , or, together with ii ) reaction of the sulfamoyl chloride of the formula III the nitrogen atom , form a 5 - to 8 -membered , saturated obtained in step i ) with ammonia , nitrogen heterocycle which , as well as the nitrogen atom , 20 the sulfamoyl chloride of the formula III being used in step may have a further heteroatom selected from O and S as a ii ) in the form of the solution obtained in step i ) in the inert ring member , where the nitrogen heterocycle is unsubsti - solvent, especially the aromatic solvent . tuted or may have 1 , 2 , 3 or 4 alkyl groups having in each The process according to the invention is associated with case from 1 to 4 carbon atoms as substituents . a series of advantages. Firstly , the process according to the Sulfuric diamides of the formula I are interesting inter - 25 invention is comparatively easy to perform . In addition , it mediates for the preparation of active ingredients , for affords the desired sulfuric diamides I in good yields, both example for the preparation of the active herbicidal ingre - based on the secondary amine used and on the sulfuryl dients described in W001/ 83459 . chloride used . The release of hydrogen chloride is substan Processes for preparing sulfuric diamides of the formula tially or even completely avoided .