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Henry Payne Phd Thesis SOME STUDIES IN HYDRIDE TRANSFER Henry Arthur Sheldon Payne A Thesis Submitted for the Degree of PhD at the University of St Andrews 1966 Full metadata for this item is available in St Andrews Research Repository at: http://research-repository.st-andrews.ac.uk/ Please use this identifier to cite or link to this item: http://hdl.handle.net/10023/15239 This item is protected by original copyright SOME STUDIES IN HYDRIDE TRANSFER A THESIS PRESENTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY of THE UNIVERSITY OP ST .ANDREWS ty- HENRY ARTHUR SHELDON PAYNE 1%6 ProQuest Number:10170817 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. ProQuest 10170817 Published by ProQuest LLC (2017 ). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, MI 48106 - 1346 Ik $3^0 ■ WLAHATION ■■ I hereby declare that the following thesis is a record of the results of experiments carried out by me, and further that the thesis is my own composition and has not previously been presented for a higher degree The research was carried out in the Department of Chemistry, St* Salvator’s College in the University of St* Andrews under the direction of Dr, D*H. Held, X certify that Henry -O* Payne has spent eleven terms at research work under my direction* that he has fulfilled the conditions of Ordinance 61 and of Ordinance 16, so that he is qualified to submit this thesis in application for the degree of Doctor of Philosophy* Director o: mrom, car@ X first matriculated, as a Clyde Henderson Bursar in Queen’s College, University of St. Andrews, in October 1956* /ifter two years of study in that College, I continued my Studies in the United College of St, Salvator and St. Leonard, St. Andrews, and subsequently graduated with Second Class Honours in June I960, I was admitted as a Research Student in the Department of Chemistxy, United College, St, Andrews in October 1960 and until October 1963 held a Maintenance Urant awarded by the Department of Scientific and Industrial Research, My research was carried out under tlw supervision of Dr,U.H. Reid, ACKnOWDCaMTS I should like to thank Dr. D,H„ Reid for his guidance and encouragement during the course of this work*- • ./-I should also like to thank the Technical' Staff of the Chemistry Department, St * Andrews for their assistance; the Shell Chemical Compary Ltd*, for their gift of oyoloheptatriene and the Department of Scientific and Industrial Research for a scholarship which made this study possible. EXPh/uWOKY NOTE This thesis is divided into three parts. Part A commences with a brief survey of the hydride-transfer reaction in its widest sense > followed by a discussion of the reagents which may act as hydride donors or acceptors* In conclusion some reactions involving quinones and amines are dealt with* Part B is a discussion of the result of a series of experiments involving oarbonium ions and high potential quinones as hydride acceptors and also of some related experiments * Part C» complementary to Part B, is devoted to the description of experimental details* x \ ? ' ' ' ' " x • r‘ • ' •*? / .SOME .STUDIES .IN, HTDRIDS TWSFER v'/'f -C • / ■ S IN D K X page A.I The Hydride-transfer Reaction.* . 1 A.II Hydride Donors. ...7 1 „ Introduction-, 2. Hydrocarbon Donors, 3. Heterocyclic Donors, 4. Natural Product Donors, 5. Alcohol and Aldehyde Donors. A,111, Hydride Acceptors. .23 1. Introduction. ' • 2* Preformed Carbonium Ions. 3. Quinones. 4< Miscellaneous Acceptors. A.IV Reactions and Interactions of Quinones with Amines. .42 1* Chemical--ReactiQns. 2. Charge-transfer Complexes. 3. Semiquinones. A. V Summaiy of Present Yfork . .52 References, . ' ' ■ ‘ - i - x Discussion B. X Dehydrogenation of hydroaromatic heterocycles using -56 Triphenylmethyl Perchlorate. B.II Dehydrogenation of hydroaromatic heterocycles using high potexitial quinones in the presence of acid. ,.61 B.III Formation of Tropylium Salts from Cycloheptatrienes using quinones in the presence of acid. ,.66 1. Introduction. 2. Dehydrogenation of Cycloheptatriene. 3. Dehydrogenation of Alkyl- and Axyleyclohept&trienes. (x) Ditropyl, ’ r (ii) ?^(Ti\iphenylmethyl) cyelcheptatriene. 4. Reactions of ?~TropyI ethers with D.D.Q, and Perchloric Acid. 7 5. Reactions ofY-Phe^lthiocycloheptatriene and 7-Cyano^ - cycloheptatriene with D.D.Q. and perchloric acid* ■?; B.1V Reactions of Cycloheptatriene and its derivatives with , A ". quinones in the absence of acid. ,,.8ly-.v' 1. Reaction of Cycloheptatriene with I).D.Q. ‘ 2. Reactions of 7~Alkyl~ and /-Arylcycioheptatrienes with D.D.q, ; - 3; Reactions of 7-^ropyl ethers and thioethers with D*D,Q. 4, Reactions of Y-himetl^Iauiinocycloheptatriene with quinones. '• ? . (i) With D.D.Q. ■ (ii) With Chloranil. • - B.V Tropylium Perchlorate as a hydride abstractor* ...104 'di B.V1 Reaction of h.D.Q. with .Tertiary Amines. '...106 - . 1, Reaction of D.D.Q. with pimethylbensylamine. ' 2. Reaction of D.D.Q. with. Trimothylamino. ■ B' .VII The Spectra of the 2 ^3*diohloro-5,6-dioyano-*1,4-bensosemiquinones, • . • - - ■.. .112-4; References, * . , ' ■«. xi'--xv-'B Experimental ' . C-.I Dehydrogenation of hydro aromatic heterocycles using the Vy Triphenylmethylcarbonium ion,. ...117.' 1, Preparation of Triphenylmethyl Perchlorate, / \ 2, Dehydrogenation of.Benso[f ]thiaohroman~4~oiie, •' (i) 4’*Hydroxy*-,1-thianaphtho[23‘1 ?b]pyrylium perchlorate, 1 (ii) Ben2o[f]thiachrom~4~one. _ /;■ 3. Deliydration-dehydrogenation of Ben^o[f]thiachroman-4*ol. { i) Benzo [f]thiachroman-4-ol. (ii) i-Thianaphtho[2,1 ,b]pyryliuni perchlorate* .' 4/Dehydrogenation of 2-thiachfoman-4-one, ' • .- ' ( i) 4~Hydroxy*"2-thiabenzo[ e ]pyrylium perchlorate, 5.. Dehydration-dehydrogenation of 2-thiachroraan~4-ol. Dehydrogenation of 5 ,6*dihydro-5^methylphenaniht'idine* . , ■ - ?; (i) Preparation and reduction of 5-raethylphenanthridinium , ■<; perchlorate. - • - , • '• (ii) Dehydrogenation with triphexxylmethyl perchlorate. 7* Dehydrogenation of $.*6~dihydro*5^6~dimethylphenanthridine, . , (i) D,G“DilTydror5,6-dimetl3ylphenanthi<dine> fT: (ii) Dehydrogenation with triphenylmethyl perchlorate. 8. Dehydrogenation of 2,3-dihydro-2,3-dimethylbenzothiazole. (i) 2,3~Pihydro~2,3-dimethylbenzotliiazole. (ii) Dehydrogenation with tfiphenylmetlxyl perchlorate, • . G.IX Dehydrogenation of hydro&romatic heterocycles using quinones ■ in the presence of acid;; ...130 7? 1, Preparation and purification of quinone reagents* \ . r : • (i) p-Chloranil. ' - ?< ( ii) ‘fetrachloro^o-bensoquinone. (o-chloranil.) .. V- (iii) 2,3-Dichloro-5,6-dicyano-1 jk^benzoquinone. (.1)J)#Q.) 2* Dehydrogenation of thiaxanthene using p-chloranil and j perchloric acid* •>/?> Dehydrogenation of thiaxanthene using D.D.Q. and perchloric acid. 4* Dehydration and dehydrogenation of benzo [f]thiachroman-4-ol " using .a-chloranil and perbhlorio acid. ’ Dehydrogenation of 5#6-dihydro-5-m©tl^rlphenanthridine using ■p-chloranil and - perchloric acid, ■ • ‘ 6, Dehydrogenation of 5 ,6-dihydrc~5 >6^dimethylphenanthridine using p-chloranil and perchloric acid. 7. Dehydrogenation of 2 ,3-dihydro-2 ^dimethylbensothiazole using p-chloranil and perchloric aoid. 8. Dehydrogenation of 2,3-dihydro-2,3-dimetty lb enzo thiazole using jCHchloranil and perchloric acid. •' '.; ■ •: • ;y- C .III Formation of-Tropylium salts from Cycloheptatrienes using quinones in the presence of acid, ...138 ; 1. Reaction of Cycloheptatriene with D.D.Q, and perchloric acid. 2. Reaction of Cycloheptatriene with o-chloranil,and perchloric acid. / Reaction of Cycloheptatriene with ^•chloranil and perchloric acid. ’ A. Reaction of Cycloheptatriene with j>~benzoquinone and perchloric acid. , 5. Reaction of Cycloheptatriene with D.D.Q. and sodium ; perchlorate. ' -'-a' ./ £>♦ Reaction of Cycloheptatriene with D.D.Q, and picric aoid. ■ -y 7. Reaction of Cycloheptatriene with D.D.Q. and lithium bromide.. 8. Reaction of Cycloheptatriene with D.D.Q. and sodium iodide, ? / 9. Reaction of Cycloheptatriene with D.D.Q, and p-toluene- sulphonic acid, . • • 10. Reaotion of Cycloheptatriene v/ith Qychl or anil and oxalic acid.- C.I7 Reactions of Alkyl- and Arylcycloheptatrienes with quinones and acid. .148 : 1. Reaction of 7-^etbyl cycloheptatriene with jq-chi or anil and —hi ■ • "perchloric' acid. .'/•* ,2. Reaction of 7~Phenylcycloheptatriene with ci-chl oranil and a? . perchloric acid. : ' ; 3; Reaotion of 7-Phenylcycloheptatriene with jq-chl oranil and sodium iodide» A* Reaction of 7“Phenylcycloheptatriene with cy chi or anil and picric acid. - . Vy 5. Reaction of Ritropyl v/ith p-’ohloranil and perchloric acid. r •- 6. Reaction of Ritropyl with Q>-chloranil and perchloric acid. 7. Reaction of Ritropyl with R.D.Q. and perchloric acid. 8. Reaction of Ritropyl-with p-bemoquinone and perchloric acid. 9. Attempted preparation and dehydrogenation of 7-(friphenyl~ ..." methyl) eye lohep tat riene, (i) Triphenylmethyl. lithium (ii) Reaction of Triphenylmetliyl lithium with Tropylium perchlorate . (iii) Analysis of the mixture and separation of the products. (iv) Attempted reactions. A G.V, Reactions of Tropyl ethers and thioethers. ...159 1. Reaction of 7“Metho3cyoycloheptatriene
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