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Photochemical Synthesis of Β-Lactones and Β- Lactams William Raymond Adams Iowa State University

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Photochemical Synthesis of Β-Lactones and Β- Lactams William Raymond Adams Iowa State University Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1967 Photochemical synthesis of β-lactones and β- lactams William Raymond Adams Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Adams, William Raymond, "Photochemical synthesis of β-lactones and β-lactams " (1967). Retrospective Theses and Dissertations. 3988. https://lib.dr.iastate.edu/rtd/3988 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]. This dissertation has been microiihned exactly as received 68—2796 ADAMS, William Raymond, 1936- PHOTOCHEMICAL SYNTHESIS OF /3 -LACTONES AND J3 -LACTAMS. Iowa State University, Ph.D., 1967 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan 0? /3-LAC20KZ3 AND /?-LACTAMS by '.Villiam RayTiOnd Adar;.3 A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of •The Requirements for the Degree of aOCTOR 0? PHII030PHY \ %ajor Subject: Organic Che:nis":ry Approved: Signature was redacted for privacy. In Chi or \/oj.'K Signature was redacted for privacy. Signature was redacted for privacy. Iowa Sta":e Univers Of Science and Technology Ames, lov/a 1967 ii TABL3 0? CONTENTS Page VITA viii INTRODUCTION 1 HISTORICAL 2 Photocycloaddition Reactions 2 Paterno-Btlchi Reaction 2 Interraolecular Photocycloaddition 3 Photochemical Decarboxylations 6 Photochemical Transformations of Acids and Related Compounds 14- R3SULTS 1S DISCUSSION 58 Spectral Considerations $8 Mechanism 61 EXPERIMENTAI, 73 Instruments 73 Procedure 73 Irradiation of cis-oC-pheny1cinnamic acid (LXXVIl) in the presence of tetramethylethylene 84 Irradiation of trans-stilbene in the presence of tetramethylethylene 85 Irradiation of cis-stilbene in the presence of tetramethylethylene 86 Irradiation of cis--phenylcinnamic acid (LXXVIl) 87 Irradiation of trans- c<-phenylcinnamic acid (LXXXVIII) 89 Thermal decomposition of cis- - diphenyl- /?-propiolactone(LXXXIII) 90 Ill Irradiation of cio- , j3-c.iphenyl- /?-propiolactone (LXXXIII) Irradiation of cis - cC , ^-diphenyl- /]- propiolactone (LX7JCIII; in the presence of t e trame thyle thylene Reaction of trans-1,2-diphenyl-3,3,4,4- tetramethylcyclobutane (LXXVIII) with bromine Reaction of trans-1,2,-diphenyl-3,3,4,4- tetramethylcyclobutane•(LXXVIII) with K- bromosuccinimide Irradiation of diphenylacetylene in the presence of tetramethylethylene Reduction of 1,2-diphenyl-3,3,4,4- tetramethylcyclobutene (LXXIX) trans- o( , /J-Diphenyl-^-propiolactone (XC) Irradiation of cis-o^-(p-tolyl)-cinnamic acid (XGIII b) Irradiation of cis-o<-phenyl-p-methyl- cinnamic acid (XCIII b) Irradiation of cis-o<-phenyl-p-chloro- 0innamic acid (XCIII d) Irradiation of cis-o<^-(p-chlorophenyl)- cinnamic acid (XCII e) Irradiation of cis-of-(p-fluorophenyl)- cinnamic acid (XCIII f) Irradiation of cis-o<-(p-cyanophenyl)- cinnamic acid (XCIII g) Irradiation of cis- -phenyl-p-cyano- cinnamic acid (XCIII h) Irradiation of cis-o<l-(p-nitrophenyl)- cinnaraic acid (XCIII i) Irradiation of cis--phenyl-^-nitro- cinnamic acid (XGIII j) iv Page Irradiation of cis-c^-phenyl-p- niethoxycinnamic acid (XCIII k) 105 Irradiation of cis- o^-( p-meth.oxyphenyl )- cinnamic acid (XCIII 1) 105 Irradiation of trans-cinnamic acid 106 Irradiation of oC-phenylorotonic acid (XCV c) 106 Irradiation of o^-methylcinnamic acid (XCV b) 107 Irradiation of ûd-phenylacrylic acid (XCV e) 108 Irradiation of crotonic acid 109 Irradiation of iX', /?-diphenylcinnamic acid (XCV d) 109 Irradiation of -phenylcinnamic acid 110 Irradiation of biphenyleneacrylic acid 111 Irradiation of cis-c<-phenylcinnamamide (CIII) 111 Irradiation of cis-o^-phenylcinnamanilide (XCVI) • 114 trans-1,3,4-Triphenyl-2-azetidinone (XCVIII) 117 SUmiARY 11 9 LITERATURE CITED 121 ACKNOWLEDGMENT 128 APPENDIX 129 V LIST OF PIGUR3S Pa^e Figure 1. Infrared spectra Top - trans-1,2-diphenyl-3,3,4,4-tetra- methylcyclobutane (LXXVIIl) in potassium bromide 23 Bottom - 1,2-diphenyl-3,3»4,4-tetramethyl- cyclobutene (LXXIX) in potassium bromide 23 Figure 2. Nuclear magnetic resonance spectra Top - trans-1,2-diphenyl-3,3,4,4-tetra- methylcyclobutane (LXXVIII) in carbon tetrachloride 25 Bottom - 1,2-diphenyl-3,3,4,4-tetramethylcyclo- "butene (LXXIX) in carbon tetrachloride 25 Figure 3» Infrared spectra Top - cis-o^-phenylcinnamic acid (LXXVIl) in potassium "bromide 32 Middle - photochemical isomerization of cis- cx:-phenylcinnamic acid (LXXVIl) to cis- oL,^ -diphenyl- /3-propiolactone (LXXXIII) in chloroform 32 Bottom - cis- PC, /?-diphenyl-/^-propiolactone '(LXXXIII) in potassium bromide 32 Figure 4. Reaction scheme 38 Figure 5. Nuclear magnetic resonance' spectra Top - cis-,/?-diphenyl-/? -propiolactone (LXXXIII) in deuteriochloroform 47 Middle - trans-1.3,4-triphenyl-2-azetidinone (XGVIII) in deuteriochloroform 47 Bottom - cis-1,3,4-triphenyl-2-azetidinone (XCVII) in deuteriochloroform 47 Figure 6. Infrared spectra Top - trans-1.3,4-triphenyl-2-azetidinone (XGVIII) in potassium bromide 49 Bottom - cis-1,3,4-triphenyl-2-azetidinone (XCVII) in potassium bromide 49 Figure 7- Infrared spectra Top - trans-3,4-diphenyl-2-azetidinone (GV) in potassium bromide 52 Bottom - cis-3,4-diphenyl-2-azetidinone (CV) in potassium bromide 52 vi Page Figure 8. Nuclear magnetic resonance spectra Top - trans-3,4-diphen.yl-2-azetidinone (CV) in deuteriochloroform 55 Bottom - cis-3,4-ciiphenyl-2-azetidinone iCIV) in deuteriochloroform 55 Figure 9. Energy level scheme for the od,/?-unsat­ urated acid system 60 vil LIST OP TABLES Table 1 . Substituent effect on -lactone formation from cis- cxl-phenylcinnamic acids Table 2. Nuclear magnetic resonance of ^-substituted cxT, (2 -diphenyl- ^-propiolactone Table 3. Charge densities of Ground, n,Pi* and Pi,Pi states Table 4. Correlation of the charge densities of the n,Pi* and Pi,Pi* excited states of the /?- carbon with irradiation times Table 5. Charge densities and bond orders of Ground, n,Pi* and Pi,Pi* excited states Table 6. Mass spectrum of cis- oC, [2 -diphenyl-/3 - propiolactone Table 7. Mass spectrum of cis-c<-(p-tolyl)-/3-phenyl- /3-propiolactone (XCIV b) Table 8. Mass spectrum of cis- o<-phenyl-/? -(p-tolyl)- /3-propiolactone (XCIV c) Table 9. Mass spectrum of cis- oi-phenyl--(p-chloro- phenyl)-/?-propiolactone (XCIII d) Table 10. Mass spectrum of trans-3,4-diphenyl-2- azetidinone (CV) Table 11. Mass spectrum of cis-3,4-diphenyl-2-azetidi° none (CIV) Table 12. Mass spectrum of 3-phenylhydrocarbostyril (CVI) Table 13. Mass spectrum of cis-1,3,4-triphenyl-2- azetidinone (XCVII) Table 14. Mass spectrum of trans-1,3,4-triphenyl-2- azetidinone (XCVHÏ) viii VITA The author was born in Niagara Palls, New York to Mr. and Mrs. William Adams, He graduated from laSalle High School in June, 1954 and was employed from 1954 to 1957 by Oldbury Elec­ trochemical Company as a laboratory and pilot plant technician. In September, 1957 he enrolled at Rochester Institute of Tech­ nology, Rochester, New York. He was granted an Associates of Applied Science degree in June, I960 and a Bachelor of Science degree in June, 1962. The author was employed in the Control Laboratories at Rochester Gas and Electric Company during his cooperative employment with Rochester Institute of Technology. In July, 1962 the author enrolled at Iowa State Univer­ sity of Science and Technology as a graduate student with a teaching assistantship. He carried out his research in the field of organic chemistry under the direction of Dr. 0. L. Chapman. The author was awarded the DuPont Teaching Award in September, 1964 and received the Master of Science degree in August, 1965. The author was graduated with the Ph.D. degree from Iowa State University of Science and Technology in August, 1967. 1 INTRODUCTION In the past ten years there has been a growing interest in light-induced transformations of organic molecules in general and conjugated ketones in particular. <<,-Unsatu­ rated ketones are known to undergo a variety of photoreactions including valence tautomerization, dimerization, cleavage, structural rearrangement and photocycloaddition. These photo- cycloadditions have proved to "be a versatile synthetic tool and have been utilized in the synthesis of cubane, caryophyl- lene, tropolones, oxetanes and cyclobutanes. The photocyclization processes have quite.recently been extended to include oC-unsaturated acids, esters, nitriles and nitro compounds, thus increasing the synthetic potential of these reactions. This thesis describes a study of the photochemistry of several «<,-unsaturated acids and amides in an effort to ex­ tend the synthetic versatility of photochemistry. 2 HISTORICAL Photocycloaddition Reactions Patemo-Btlchi Reaction Formation of oxetanes by photocycloaddition of aldehydes and ketones to olefins provide an attractive entry into small ring heterocyclic systems. Irradiation of benzophenone in the presence of excess isobutylene gives only two oxetanes (I and II) in high yield (1,2,3,4). 0 hty cr 0— y % II 90^ The reactions involve the n,?i* triplet state of the car- bonyl system and the predominant isomer is correctly predicted from consideration of the more stable biradical (ground state) intermediate. A large number of such reactions are
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