Nucleophilic displacement at carbon bearing nitrogen Item Type text; Dissertation-Reproduction (electronic) Authors Swedo, Raymond John, 1948- Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 04/10/2021 13:58:52 Link to Item http://hdl.handle.net/10150/565380 NUCLEOPHILIC DISPLACEMENT AT CARBON BEARING NITROGEN by Raymond John Swedo A Dissertation Submitted to the Faculty of the DEPARTMENT OF CHEMISTRY In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY In the Graduate College' THE UNIVERSITY OF ARIZONA 1 9 7 7 THE UNIVERSITY OF ARIZONA GRADUATE COLLEGE I hereby recommend that this dissertation prepared under my direction by _______ Raymond John Svedo___________________________ _ entitled Nucleophilic Displacement at Carbon Bearing__________ Nitrogen_____________________________________________ be accepted as fulfilling the dissertation requirement for the degree of Doctor of Philosophy Dissertation Director Date As members of the Final Examination Committee, we certify that we have read this dissertation and agree that it may be presented for final defense. Final approval and acceptance of this dissertation is contingent on the candidate's adequate performance and defense thereof at the final oral examination. STATEMENT BY AUTHOR This dissertation has been submitted in partial fulfillment of requirements for an advanced degree at The University of Arizona and is- deposited in the University Library- to be made available to borrowers under rules' of the Library. Brief quotations from this dissertation are allowable without special permission, provided that accurate acknowledgment of source, is made„ Requests for permission for extended quotation from or reproduc­ tion of this manuscript in whole or in part may be granted by the head of the major department or the Dean of the Graduate College when in his judgment the proposed use of the material is in the interests of scholarship. In all other instances, however, permission must be obtained from the author. SIGNED; TABLE OF CONTENTS Page LIST OF TABLES ......... , . ix LIST OF ILLUSTRATIONS xi ABS TRACT ......................... , . xii INTRODUCTION ^ 1 RESULTS AND DISCUSSION ^ . 4 SUMMARY , ......... 54 EXPERIMENTAL ^ . 58 Preparation of Trifluoromethanesulfonic Acid Anhydride . 60 Preparation of N^-Alkyl- and N , N-D ia Ikyl tr i c hi or o— me thane sul f enami.des: .............. 60 Preparation of Sulfonamides: . ^ . 61 Procedure A ....................... 61 Procedure B ....................... ....... 61 Procedure C . ....................... 62 Procedure D ' ..... 62 Procedure E . ............... 62 Procedure. F 63 Procedure G ^ . ^ 64 Procedure H........ .......... 64 Procedure I ^ ^ ^ , 64 Procedure J ............. 65 Preparation of N-Sulfenyl-N-sulfonamides........... 65 Procedure A ................. 65 Procedure B ..................... 6 6 Procedure C ................. 67 Procedure D ................ 67 Preparation of Sulfonimides ................ 6 8 Procedure A ...................... 6 8 Procedure B ..... ....... 6 8 Procedure C ............ 69 Attempted Preparation of N-n-Hexyl-N, N-di- Ctrichlorome thane)' sulf enimide .............. 70 From ii-Hexylamine ................... 7Q From N-nj-Hexy 1 trie hlorome thane sul f enami de . 70 lii iv TABLE OF CONTENTS— Continued Page Attempted Preparation of N-n-^Hexyl-N,N-di-r- (trichlorome thane ysulfonimide . «. ......... 71 From N-ri-Hexyl-N, N-di (trichloromethane)"sulfenimide . 71 From N-nyHexyl-N- (Trichloromethanesulfenyl )'- trichlorome thanesulfonamide . , « . 72 Preparation of Ethyl Ethoxyacetate 74 Preparation of 3—nyHexyl-2, 4*^pentanedione and 2, 4^ Pentanedione n-Hexyl Enol Ether . 75 Preparation of n^Hexyl Phenyl Sulfide 75 Preparation of Barium Trichloromethanesulfonate ......... 76 Preparation of Potassium Trichlorome thane sulfonate....... 76 Preparation of Trichloromethanesulfonic A c i d ............. 77 Preparation of Trichloromethanesulfonic Acid Anhydride . 77 Procedure A . ................................. 77 Procedure B ......................... 78 Reaction of N, N-Di^iso^propyltrichloromethane-^ sulfenamide with. Ozone . ^ . % . .. , . , . t 78 Reaction of N-nyHexyl trichlorome thane sulfenamide with Active Manganese Dioxide ............................... 79 Attempted Preparation of N-sec -Butyl-N- (trie hlorome thane - sulfonyl)trifluoromethanesulfonimide ................... 79 Procedure A ......... 79 Procedure B ......................................... 80 Attempted Preparation of N-n-Hexyl-N- Ctrichloromethane- sulfonylItrifluoromethanesulfonimide . ...... 80 From NvUy-Hexy 1 ^N- (trichloromethanesulfenyl) - trif luorome thanesulfonamide t .... 80 From N-nyHiexyl trif luorome thanesulfonamide. >. 81 From N^-nyHexyl trie hlorome thanesulfonamide 82 Attempted Preparation of N^-t-Butyl-N, N-di (benzene)- sulfonimi.de . 82 Procedure A ^ «•••». ..o ® . ^ ^ 82 Procedure B . ...... » . 82 Procedure C ^ r . 83 Attempted Preparation of N-l^Adamantyl-N,N^- di (benzene.r.sulfonimide ..... t ^ ^ . 83 Attempted Preparation of N^ C4-Ni.tr op he ny 1)-N-^ benzyl tri f luo rome thane sul f onamide . „ . ^ . ^ . *. 84 Sulfonylation of N^ [4-Nitrophenyl) -N^benzylamine . 84 Nitration of N-Phenyl-N-benzyl (trif luorome thane )"- sulfonamide . ^ . 85 Sulfonylation of 4^Nitroaniline, Followed by Alkylation e ... ....... 87 Attempted Preparation of 3-Benzyl—3-trif luo rome tha ne­ sulf ony 1-1 ^phenyl triazene . » . ^ ..... ^ . ... 87 Procedure A ............. 87 Procedure B ................................. 8 8 V TABLE OF CONTENTS— Continued Page Attempted Preparation of 3-ri-Hexy 1 - 3- trifluoromethane- sulfonyl-l-phenyltriazene .......... 8 8 Procedure A ........... 8 8 Procedure B ................ 8 8 Attempted Preparation of 3-Methyl^3-trifluoromethane- sulfonyl-l-p^tolyltriazene ......... 89 Reaction of Triehloromethanesulfonic Acid Anhydride with Benzyfamine . 89 Reaction of Tc ic hlorome thane sulfonic Acid Anhydride with n-Hexy 1 am i n e ........................................... 89 Reaction of Trie hlorome tha ne sul f ony 1 Chloride with Phenol ...................................... 90 Reaction of Trichloromethanesulfonyl Chloride with Sodium Phenol ate ........ .. .... 90 Reaction of Trichloromethanesulfonyl Chloride with Silver Tri fluo rome tha ne sulfona te . * . * . » . , 91 Reactions of N^-Cyano-N-phenyltrifluoromethane- sulfonamide with Sodium di-^t-butylphenolate ...... t ^ 92 Procedure A ........................................ 92 Procedure B . ......... ^ . 92 Reaction of N-Cya no -N-phe nyl tr i f luo r ome tha ne-^ sulfonamide with Sodium Phenolate . .. 93 Reaction of N ^Cya no -N -p he nyl tr i f luo rome thane - sulfonajni.de with HMPT ........... 94 Reaction of N-Cya no-N-p he nyl tr if luo rome thane- sulfonamide with -CH^CN......... e s .. 95 Reaction of N-Cya no -N-hexy 1 tr i f luo rome tha ne- sulfonamide with Diethyl Sodioma Iona te . % . , . 95 Reaction of N-u-Hexyltrifluoromethanesulfonamide with. 2 r-Ca r Borne thoxy-1 -c yc lope n te nyl -1 -trif luo rome tha ne ^ sulfonate . .......... 96 Reaction of N f N-di-n-Hexyltrif luo rome thane sulfonamide with 2TrCarbomethoxycyclopentanone Potassium Salt .... 97 Reac tion of 2-n-Hexylr-2-ca! rbome thoxyc yc lope nta none with. 2-Ca rbome thoxyc yc 1 ope nta no ne Potassium Salt . , , 97 Reaction of N f N-di^iso-Pr op yl trif luor ome thane— sulfonamide with Diethyl Sodioma lo na te ... s . 98 Reaction of N-rPhenyl-N-benzyltrifluoromethane— sulfonamide with One Equivalent. of Sodium Cyanide . 99 Reaction of N-Phenyl-N-benzyl trif luo rome thane— sulfonamide with Excess Sodium Cyanide. .... * . 99. Reaction of N-Phenyl-N-benzyl trif luo romethane— sulfonamide with Excess Diethyl So dioma Iona te . 100 Reaction of N-C4-Fluorophenyl)>N-benzyi Ctrif luorome, thane I- sulfonamide with Excess Diethyl Sodioma Iona te . .... 100 vi TABLE OF CONTENTS— Continued Page Reaction of Various N-Alkyl-N, N-di (trifluoromethane) - sulfonimides with Sodium Cyanide in HMPT 101 Reaction of Various N-Alkyl-N/N-diCtrifluoromethane)- sulfonimide.s with Potassium Iodide in HMPT 102 Reaction of Various N-Alkyl-N, N-di Ctrifluoromethane.} ^ sulfonimides with Diethyl Sodioma 1 onate in HMPT . ^ . 103 .Reaction of N-Benzyl-N,N-di Ctrifluoromethane}.-. sulfonimide with Potassium Acetate in HMPT . , . 104 Reaction of N-_n-Hexyl-N,N-di (trifluoromethane} ^ sulfonimide with .Various Nucleophiles in HMPT . t . 105 Reaction with 2-Carbomethoxycyc 1 opentanone Potassium Salt . ^ . 105 Reaction with Ethyl Sodioac e toac e ta te » . , . 106 Reaction with Potassium Acetate % % . 107 Reaction with Sodium Thiophenoxide 108 Reaction with Sodium Azide . - . ....... « • 109 Reaction with Ac etylacetona to thallium (1} . 109 Reaction with Malononitrile Sodium Salt ............ 110 Reactions with Phenyl Magnesium Bromide . ....... Ill Reactions with Water.......... 112 Reactions with HMPT . 116 Reactions of N-n^Hexyl-N,N^di Ctrifluoromethane) ^ sulfonimide with Various Nucleophiles, via the Tris Cdimethylamino)-n.-hexyloxyphosphonium Salt CVIT) in H M P T ......... ............. 118 Reaction with Sodium Cyanide .......... 119 .Reaction with Diethyl Sodiomalonate ......... 120 Reaction with Malononitrile Sodium Salt ........ 121 •Reaction with