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Studies of Properties of Derivatives of 1-Phospha-5-Aza-2,6,9-Trioxabicyclo[3.3.3]

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Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1983 Studies of properties of derivatives of 1-phospha-5-aza-2,6,9-trioxabicyclo[3.3.3]undecane and structurally related molecules Leslie Earl Carpenter II Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Inorganic Chemistry Commons Recommended Citation Carpenter, Leslie Earl II, "Studies of properties of derivatives of 1-phospha-5-aza-2,6,9-trioxabicyclo[3.3.3]undecane and structurally related molecules " (1983). Retrospective Theses and Dissertations. 8457. https://lib.dr.iastate.edu/rtd/8457 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. INFORMATION TO USERS This reproduction was made from a copy of a document sent to us for microfilming. While the most advanced technology has been used to photograph and reproduce this document, the quality of the reproduction is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help clarify markings or notations which may appear on this reproduction. 1. The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting through an image and duplicating adjacent pages to assure complete continuity. 2. When an image on the film is obliterated with a round black mark, it is an indication of either blurred copy because of movement during exposure, duplicate copy, or copyrighted materials that should not have been filmed. For blurred pages, a good image of the page can be found in the adjacent frame. If copyrighted materials were deleted, a target note will appear listing the pages in the adjacent frame. 3. When a map, drawing or chart, etc., is part of the material being photographed, a definite method of "sectioning" the material has been followed. It is customary to begin filming at the upper left hand comer of a large sheet and to continue from left to right in equal sections with small overlaps. If necessary, sectioning is continued again—beginning below the first row and continuing on until complete. 4. For illustrations that cannot be satisfactorily reproduced by xerographic means, photographic prints can be purchased at additional cost and inserted into your xerographic copy. These prints are available upon request from the Dissertations Customer Services Department. 5. Some pages in any document may have indistinct print. In all cases the best available copy has been filmed. Universi^ Miomlrns International 300 N. Zeeb Road Ann Arbor, Ml 48106 8407056 Carpenter, Leslie Earl, II STUDIES OF PROPERTIES OF DERIVATIVES OF 1-PHOSPHA-5-AZA-2,6,9- TRIOXABICYCLO(3.3.3)UNDECANE AND STRUCTURALLY RELATED MOLECULES Iowa State University PH.D. 1983 University Microfilms Intornâtional aOON.Zeet Road, Ann Arbor, Ml 48106 PLEASE NOTE: In all cases this material has been filmed in the best possible way from the available copy. Problems encountered with this document have been identified here with a check mark V . 1. Glossy photographs or pages 2. Colored illustrations, paper or print 3. Photographs with dark background 4. Illustrations are poor copy 5. Pages with black marks, not original copy 6. Print shows through as there is text on both sides of page 7. Indistinct, broken or small print on several pages l/^ 8. Print exceeds margin requirements 9. Tightly bound copy with print lost in spine 10. Computer printout pages with indistinct print 11. Page(s) lacking when material received, and not available from school or author. 12. Page(s) seem to be missing in numbering only as text follows. 13. Two pages numbered . Text follows. 14. Curling and wrinkled pages 15. Other University Microfilms International Studies of properties of derivatives of l-phospha-5-aza-2,6,9-trioxabicyc1o[3.3.3]undecane and structurally related molecules by Leslie Earl Carpenter II A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY Department: Chemistry Major: Inorganic Chemistry Approved: Signature was redacted for privacy. Signature was redacted for privacy. For tne Major uepartm^ Signature was redacted for privacy. Iowa State University Ames, Iowa 1983 ii TABLE OF CONTENTS Paae ABSTRACT xx PART I: CRYSTAL AND MOLECULAR STRUCTURE OF 3,9-DIMETHOXY- 2,4,8,lO-TETRAOXA-3,9-DIPHOSPHA SPIRO[5.51UNDECANE 1 INTRODUCTION 2 EXPERIMENTAL 4 RESULTS AND DISCUSSION H PART II: CRYSTAL AND MOLECULAR STRUCTURE OF 2-0X0-2(BIS-(g- CHL0R0ETHYL)AMIN0)-4,6-DIMETHYL-l,3,2- OXAZAPHOSPHOR INANE 14 INTRODUCTION 15 EXPERIMENTAL 18 RESULTS AND DISCUSSION 28 PART III: BICYCLIC TO TRICYCLIC TRANSFORMATIONS IN 1-PHOSPHA- 5-AZA-2,6,9-TRI0XABICYCL0[3.3.3 lUNDECANE SYSTEMS 33 INTRODUCTION 34 EXPERIMENTAL 36 . RESULTS AND DISCUSSION 48 PART IV: 1^0 NMR OF PHOSPHITES AND PHOSPHATES 68 INTRODUCTION 69 EXPERIMENTAL 74 RESULTS AND DISCUSSION 83 PART V: ATTEMPTED SYNTHESIS OF "ATRAPE" CAGES 118 INTRODUCTION 119 EXPERIMENTAL 120 RESULTS AND DISCUSSION 127 i i i PART VI: PROTONATION OF l-PH0SPHA-5-AZA-2,6,9- TRIOXABICYCLO[3.3.3 lUNDECANE 129 INTRODUCTION 130 EXPERIMENTAL 131 RESULTS AND DISCUSSION 135 SUMMARY 137 REFERENCES 138 ACKNOWLEDGEMENTS 154 iv LIST OF TABLES Page Table 1. Calculated and observed structure factors for 3,9-dimethoxy-2,4,8,10-tetraoxa-3,9-diphospha-spiro [5.5]undecane 6 Table 2. 3,9-Dimethoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5]undecane final atomic and positional parameters 8 Table 3. 3,9-Dimethoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5]undecane final thermal parameters 9 Table 4. 3,9-Dimethoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.51undecane intramolecular bond distances and angles 10 Table 5. Calculated and observed structure factors for 2-Oxo-2-(b i s -(6-ch1oroethy1)ami no)-4,6-d imethy1 - 1,3,2,-oxaza-phosphorinane 20 Table 5. 2-0xo-2-(bis-(6-chloroethyl)amino)-4,6-dimethy^- l,3,2-oxaza-phosphorinane final atomic and positional parameters 24 Table 7. 2-0xo-2-(bis-(G-chloroethyl)amino)-4,6-dimethyl- 1,3,2-oxaza-phosphorinane final thermal parameters 25 Table 8. 2-0xo-2-(bis-(6-chloroethyl)amino)-4,6-dimethyl- 1,3,2-oxaza-phosphorinane intramolecular bond distances and angles 26 Table 9. 2-0xo-2-(bis-(6-chloroethyl)amino)-4,6-dimethyl- 1,3,2-oxaza-phosphorinane torsional and interplanar angles 27 Table 10. and NMR data for the protonation of phosphatrane oxide (20) with trifluoroacetic acid — 52 Table 11. and ^^P NMR data for the protonation of phosphatrane sulfide (21) with trifluoroacetic acid 77 58 V Table 12. and NMR data and Vn_Q for complexes of phosphatrane oxide with BFo, EtoSiClO^ and Zn(C104)2 64 Table 13. IR and UV data for cobalt complexes of phosphates... 65 Table 14. ^^0 NMR chemical shifts and coupling constants of phosphites 84 Table 15. ^^0 NMR chemical shifts and coupling constants of phosphates 91 Table 16. and NMR data for cyclic phosphites 98 Table 17. and NMR data for cyclic phosphates 105 Table 18. Dipole moments of cyclic phosphates 106 Table 19. Slopes, intercepts, and correlation coefficients for plots of (S^'O versus <S^^P for phosphates 112 VI LIST OF FIGURES Page Figure 1. Computer drawing of 3,9-dimethoxy-2,4,8,10-tetraoxa- 3,9-diphosphaspiro [5.5]undecane 12 Figure 2. Computer drawing of 2-oxo-bis(2-B-(chloroethyl) ami no)-4,6-dimethy1-1,3,2-oxazaphosphor inane 29 Figure 3. NMR spectrum of methylene group adjacent to nitrogen in initial attempt at protonation of phosphatrane oxide (^) 49 Figure 4. NMR spectrum of monoprotonated phosphatrane oxide (20) 53 Figure 5. NMR spectrum of diprotonated phosphatrane oxide (^) 55 Figure 6. NMR spectrum of phosphatrane sulfide as a function of temperature 60 Figure 7. Plot of ^^P chemical shift versus the ^^0 chemical shift of the phosphoryl oxygen of phosphates 110 Figure 8. Plot of ^^0 chemical shift of the phosphoryl oxygen of phosphates versus Jpse of the corresponding selenophosphates. ,v 114 Figure 9. Plot of ^^P chemical shift of cyclic phosphates against Jpcg of the corresponding selenophosphates 116 VI1 Compounds discussed in thesis: 0 ' 0 vi i i V- OMe OMe (C1CH2CH2)2N. H P- CICHgCHgNx^/^N 6 CNz 0 CH, Cl (ClCH2CH2)2N\p.^ -N- CH. CH. Cl ix MeOjSOCHjCHjN 12 CH, CH, CI 13a N(CH2CH2C1)2 13b (CH2CH2C1)2N>^p'^[} 0— 14 o=^//!i- I N(CH2CH2C1)2 Ph Me,N 15 0^ Xn/-" Se A- 15 xi 20 0=P, 'oS». / 21 S-»P 0 22 Se=P. 'oS, / 23 ^ \ï / 24 (OOgMoP^ '0>S xn /" 25 (OOjWP 25 27 PtCljCNCPfDj 28 P(0Me)3 P(0Et)3 30 P(0Ph)3 31 P(0-i-Pr)3 32 PCO-i-Bujj 33 I OMe 34 OEt X111 OPr 0-i-Pr I 0-i-Bu OPhI OMe xiv OMe 42a L OMe MeO. /^O- 42b >P 43a I OMe OMe XV 0 45 P 1 OMe 46 47 48 49 OP(OMe), 50 OP(OEt), 51 OP(O-i-Pr) 52 OP(O-i-Bu) xvi OEt I OMe xvi i MeO\ / 58b I V 0^/ 59a OMe 59b 60 OMe 61 \ //»• 62a OMe XVI1i MeO.
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  • Synthesis and Characterization of Seven Thiophosphate

    Synthesis and Characterization of Seven Thiophosphate

    SYNTHESIS AND CHARACTERIZATION OF SEVEN THIOPHOSPHATE ANALOGS OF CYCLIC DIGUANOSINE MONOPHOSPHATE by JIANWEI ZHAO A Dissertation submitted to the Graduate School-New Brunswick Rutgers, The State University of New Jersey in partial fulfillment of the requirements for the degree of Doctor of Philosophy Graduate Program in Chemistry and Chemical Biology written under the direction of Professor Roger A. Jones and approved by ________________________ ________________________ ________________________ ________________________ New Brunswick, New Jersey [May, 2009] ABSTRACT OF THE DISSERTATION SYNTHESIS AND CHARACTERIZATION OF SEVEN THIOPHOSPHATE ANALOGS OF CYCLIC DIGUANOSINE MONOPHOSPHATE by JIANWEI ZHAO Dissertation Director: Professor Roger A. Jones Cyclic diguanosine monophosphate (c-di-GMP) was first identified as an activator of bacterial cellulose synthase in 1987. Since then, it has been recognized as an important second messenger molecule in many bacterial processes, including cellulose synthesis, biofilm formation, and host-pathogen interactions. More recently, it found to stimulate innate immunity in mammals. The monothiophosphate analog was synthesized some years ago and was shown to be a highly potent activator/second messenger with a high stability to enzymatic degradation. In the work presented here, synthetic methods have been developed to synthesize mono-, di- and trithiophosphate c-di-GMP analogs. All seven diastereomers of these analogs have been separated and purified. Stereochemistry of the two diastereomers of ii the monothioate analog was assigned by enzymatic digestion of the linear dimer, as well as direct enzymatic degradation of the cyclic dimers. In addition, the same linear dimer was cyclized to produce a cyclic dimer of known configuration. The correlation between stereochemistry and 31P NMR chemical shifts of the two diastereomers of the monothioate was then used to assign configurations of the di- and trithiophosphate analogs.