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Tetraphenylporphyrin dimers and their derivatives Zingoni, Jesmael P. 1979

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TETRAPHENYLPORPHYRIN DIMERS AND THEIR DERIVATIVES by JESMAEL P. ^ ZINGONI B.Sc, University of Zambia, 1975 A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE i n T H E F A C U L T Y O F G R A D U A T E S T U D I E S i n the Department of Chemistry We accept t h i s thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA May, 1979 Ci^Jesmael P. Zingoni In p r e s e n t i n g t h i s t h e s i s i n p a r t i a l f u l f i l m e n t o f the r e q u i r e m e n t s f o r an advanced degree a t the U n i v e r s i t y o f B r i t i s h C o l u m b i a , I a g r e e t h a t the L i b r a r y s h a l l make i t f r e e l y a v a i l a b l e f o r r e f e r e n c e and s t u d y . I f u r t h e r a g r e e t h a t p e r m i s s i o n f o r e x t e n s i v e c o p y i n g o f t h i s t h e s i s f o r s c h o l a r l y p u rposes may be g r a n t e d by the Head o f my Department o r by h i s r e p r e s e n t a t i v e s . I t i s u n d e r s t o o d t h a t c o p y i n g o r p u b l i c a t i o n o f t h i s t h e s i s f o r f i n a n c i a l g a i n s h a l l not be a l l o w e d w i t h o u t my w r i t t e n p e r m i s s i o n . Department o f , CMSTRY The U n i v e r s i t y o f B r i t i s h Columbia 2075 Wesbrook P l a c e V a n c o u v e r , Canada V6T 1W5 i w is , 1979 ( i i ) ABSTRACT Tetraphenylporphine (TPP) and i t s para-methyl d e r i -vative have been synthesized by direct reaction of pyrrole with the corresponding aldehyde. The synthesis of two unsymmetrically substituted tetraarylporphyrins i s re-ported. The compounds prepared are' 5-(^-hydroxypheny1) - 1 0 , 1 5 j 2 0 - t r i t o l y I p o r p h y r i n and 5-(^-hydroxypheny1)-10, 1 5 } 2 0 -triphenyIporphyrin. The sy thesis of covalently linked porphyrin dimers, joined via ether linkages, i s described. High yields of the tetraaryIporphyrin dimers were obtained by the reac-tion of the bi-functionall,6-ditosyloxyhexane with phenolic porphyrins such as 5 -(^-hydroxypheny 1 ) - 1 0 , 1 5 , 2 0-tritoly 1 - " porphyrin. The dimeric porphyrins were then chromatograph-i c a l l y separated from the unreacted monomericLporphyrins , The reduction of the porphyrins(monomers and dimers) has been carried out using the standard diimide precursor, p-toluenesulfonylhydrazine. We have been able to demon-strate that the most e f f i c i e n t c h l o r i n preparation i n -volves the diimide reduction of a tetraaryIporphyrin to the corresponding b a c t e r i o c h l o r i n , followed by the ad-d i t i o n of the "high potential quinone" DDQ, to dehydro-genate the bacteriochlorin. A detailed study of the absorption spectra of these chlorins and bacteriochlo-r i n s was undertaken. Zinc metallo-derivatives of the porphyrins, chlorins and bacteriochlorins were prepared by the reaction of the free bases with zinc acetate in dry pyridine. ( i i i ) An attempt was made to s y n t h e s i z e tetra-meso- [p, p ' - ( 3 , 3 '-phenoxypropoxypheny1)]-s t r a t i - b i s p o r p h y r i n (Compound X X ) , a novel cyclophane system composed of two opposed, c o - a x i a l p o r p h y r i n r i n g s , r i g i d l y h e l d together by p e r i p h e r a l ether l i n k a g e s . The s y n t h e s i s was attempted by c o n s t r u c t i o n of a second p o r p h y r i n r i n g on top of a p r e - e x i s t i n g one, by way of the condensation of fo u r p y r r o l e s with a t e t r a a l d e h y d e , d e r i v a t i v e of t e t r a p h e n y l -p o r p h y r i n , under high d i l u t i o n c o n d i t i o n s . The l a s t r e a c t i o n step was u n s u c c e s s f u l . The s t r u c t u r e s and p u r i t y of the i n t e r m e d i a t e compounds l e a d i n g to the s t r a t i - b i s -p o r p h y r i n were e s t a b l i s h e d by mass spectroscopy and proton n.m.r. spectroscopy. ( i v ) ACKNOWLEDGEMENTS I would l i k e to express my g r a t i t u d e to my Research Ad v i s o r , P r o f e s s o r David D o l p h i n , f o r i n t r o d u c i n g me to the very important f i e l d of Porphyrin Chemistry. I would a l s o l i k e to thank a l l the students I know, who have been or are i n Dr. Dolphin's r e s e a r c h l a b o r a t o r i e s , f o r the u s e f u l chemical d i s c u s s i o n s we have engaged i n . I would l i k e to acknowledge the U.E.C. Chemistry Department f o r g i v i n g me the opp o r t u n i t y to teach. Barb, my w i f e , deserves s p e c i a l a p p r e c i a t i o n f o r general support and encouragements. (v) TABLE OF CONTENTS PAGE TITLE ' (1) 'ABSTRACT ( i i ) ACKNOWLEDGEMENTS ( iv ) ABBREVIATIONS ( ix ) STRUCTURE AND NOMENCLATURE (x) INTRODUCTION 1 DISCUSSION 29 CONCLUSIONS ^6 EXPERIMENTAL 50 PART (A) - SUBSTITUTED TETRAPHENYLPORPHYRINS - (MONOMERS AND DIMERS ) 52 meso-Tetraphenylporphyrin 52 meso-Tetratoly Iporphin 53 5_(^-Hydroxypheny1)-10 j15 j 2 0 - t r i t o l y l p o r p h y r i n 55 5_ (ij-Hydroxyphenyl ) -10,15, 20-tripheny lporphyrin 57 Preparation of 1,6- Mtosyloxyftes_ne 58 1, 6-Bte-para-formylphenoxyhexane 60 l-Hydroxy-6-para-formylphenoxyhexane 61 5_ [(lj_ (6-Hydroxy-l-hexoxy )phenyl] -10,15 ,20-t r i t o l y lporphyrin 63 5,10,15-Tri-p-anisy1-20- [4- [ 6 -[p-(10, 1 5 , 2 0-tri-p-anisy1-5-porphinyl)phenoxy]hexoxy]phenyl]porphine.... 65 5,10,15-Tri-p-toly1-20- [4-[6- [p-(10,15,20-tri-p-toly1-5-porphinyl)phenoxy]hexoxy]phenyl]porphine 68 5,10,15-Triphenyl-20- [*•- [6-(10,15,20-tripheny 1-5-p o r p h i n y l ) p h e n o x y ] h e x o x y ] p h e n y l ] p o r p h i n e 72 (vi) PAGE PART CB) - TETRAPHENYLBACTERIOCHLORINS AND CHLORINS (MONOMERS AND DIMERS) 75 weso-Tetraphenylbacteriochlorin 75 meso-Tetrapheny I c h l o r l n 77 5_ [4-(6-Hydroxy-l-hexoxy)phenyl] -10,15 ,20-t r i t o l y l b a c t e r i o c h l o r i n 79 5_ [4_(6-Hydroxy-l-hexoxy)phenyl]-10,15,20-t r i t o l y l c h l o r i n 81 5 , 1 0 , 1 5-Tri-p-tolyl - 2 0 - [M- [6- [p- ( 1 0 , 1 5 , 2 0-tri-p-toly 1 - 5-bacteriochlorinyl)phenoxy]hexoxy]phenyl] bacteriochlorin 82 5 , 1 0 , 1 5-Tri-p-tolyl - 2 0 - [ 4 - [ 6 - [p-( 1 0 , 1 5 , 2 0-tri-p-tolyl - 5-chlorinyl)phenoxy]hexoxy]phenyl]chiorin 8 M PART (C) - ZINC METALLO-DERIVATIVES OF THE MESO-TETRAPHENYLPORPHYRINS, CHLORINS AND BACTERIOCHLORINS (MONOMERS AND DIMERS) 86 Zinc Tetraphenylporphin 86 Zinc Tetrapheny lporphin Dimer 88 Zinc Tetraphenylchlorin 89 Zinc Tetraphenylchlorin Dimer 91 Zinc Tetrapheny l b a c t e r i o c h l o r i n 92 Zinc Tetrapheny l b a c t e r i o c h l o r i n Dimer 9^ PART (D) - ATTEMPTED SYNTHESIS OF TETRA-MESO- [p,p'-(.3 , 3 ' -PHENOXYPROPOXYPHENYL)] -STRATI-BIS-PORPHYRIN 96 p- 3-Bromopropoxybenzaldehyde 96 ( v i i ) PAGE 5,10,15,20-Tetra-[p-(3-bromopropoxy)phenyl]-porphyrin 98 5,1 0 ,15,2 0-Tetra-(4-propionylphenyl)porphyrin 101 5 ,10,15,20-Tetra-(4-hydroxyphenyl)porphyrin 103 5 , 10 ,15,20-Tetra-[(p 1-formyl -3-phenoxy-p-propoxy)phenyl] porphyrin 105 Tetra-meso- [p,p'-(3,3'-phenoxypropoxyphenyl)-B tra ti-fcisporphyr in 106 REFERENCES 108 OPTICAL SPECTRAL APPENDIX 117 ( v i i i ) OPTICAL SPECTRAL APPENDIX P A G E TetraphenyIporphine (Monomer) 118 5_ (6-Hydroxy-l-hexoxy) phenyl]-10,15, 20-t r i t o l y Iporphyrin 119 Tetrapheny Iporphine (Dimer) 120 Tetraphenylchlorin (Monomer) 121 Tetraphenylchlorin (Dimer) 122 Tetrapheny l b a c t e r i o c h l o r i n (Monomer) 123 Tetrapheny l b a c t e r i o c h l o r i n (Dimer ) 12^ Zinc Tetrapheny Iporphine (Monomer) 125 Zinc Tetrapheny Iporphine (Dimer) 126 Zinc Tetraphenylchlorin (Monomer) 127 Zinc Tetraphenylchlorin (Dimer) 128 Zinc Tetrapheny l b a c t e r i o c h l o r i n (Monomer) 129 Zinc Tetraphenylbacteriochlorin (Dimer) 130 ( i x ) ABBREVIATIONS In t h i s work the terms p o r p h y r i n , porphine and porphin are used i n t e r c h a n g e a b l y . A b b r e v i a t i o n s which may occur without d e f i n i t i o n i n c l u d e : Abs. = = Absorbance ATP = = Adenosine Triphosphate DDQ = = 2 , 3-Dichloro - 5 , 6-dicyanobenzoquinone DKF = = N,N-dimethylformamide EPE = = E l e c t r o n Paramagnetic Resonance Hz = Hertz ( c y c l e s per second) I = I n t e n s i t y L i t . = = L i t e r a t u r e M.W. = = M o l e c u l a r Weight Ref. = = Reference TFA = = T r i f l u o r o a c e t i c a c i d TPBC = = me s o - T e t r a p h e n y l b a c t e r i o c h l o r i n TPC = = mes o - T e t r a p h e n y l c h l o r i n TPP = = me so-TetraphenyIporphyrin ( x ) STRUCTURE AND NOMENCLATURE The nomenclature (a) i s t h a t recommended f o r t e t r a -p y r r o l i c m a c r o c y c l e s by IUPAC r u l e s f o r n o m e n c l a t u r e , J . Amer. Chem. Soc. 8 2 , 5582 ( I 9 6 0 ) . I n t h i s t h e s i s t he p r o t o n s 2 , 3 , 7 , 8,12 , 1 3 , 1 7 , 1 8 are r e f e r r e d t o as the 6 - p y r r o l e p r o t o n s . The carbons 1,4, 6 ,9,11,14,16 , 19 are the a-carbons. The p o s i t i o n s 5,10, 15,20 are the m e s o - p o s i t i o n s . -1 -INTRODUCTION (a) N a t u r a l occurence and Importance of p o r p h y r i n dimers and aggregates. . P o r p h y r i n aggregates play an important r o l e i n both 1 2 p h o t o s y n t h e t i c and metabolic p r o c e s s e s . ' The biosphere depends upon p h o t o s y n t h e s i s to c a r r y out the c o n v e r s i o n of photonic i n t o chemical energy as w e l l as to maintain an o x i d i z i n g atmosphere f o r c a t a b o l -ism ( c o n v e r s i o n of organic compounds to C 0 2 ) which pro-vides the energy necessary to d r i v e endergonic b i o c h e m i c a l processes. The c l a s s i c a l r e a c t i o n of p h o t o s y n t h e s i s r e q u i r i n g c h l o r o p h y l l - a (2) i n v o l v e s C 0 2 f i x a t i o n , namely C 0 2 + H 20 -> [CH 20] + 0 2 (1) ( l i g h t , c h l o r o p h y l l ) a carbohyd: o x i d i z a b l e hydrogen donor. where [CH^O] i s carb rate and water serves as the H. C & R C C L C H ? (2) (3) A r e a c t i o n s i m i l a r t o (1) occurs i n p h o t o s y n t h e t i c b a c t e r i a which u t i l i z e b a c t e r i o c h l o r o p h y l l (3) and hydrogen - 2 -donors o t h e r t h a n w a t e r . The p h o t o s y n t h e t i c p r o c e s s d i v i d e s n a t u r a l l y i n t o 3 ^ l i g h t - d r i v e n p r i m a r y r e a c t i o n s ' and t h e subsequent CO^ r e d u c t i o n s t e p s s t u d i e d by C a l v i n , Bassham, and 5 c o w o r k e r s . Under the t i t l e o f p r i m a r y r e a c t i o n i s i n -c l u d e d t h e c o n v e r s i o n o f l i g h t energy i n t o r e d u c t a n t s and o x i d a n t s and , i n t he case o f g reen p l a n t s and b l u e - g r e e n a l g a e , t he c h e m i c a l and p h y s i c a l s t a t e s i n v o l v e d i n t he o x y g e n - e v o l v i n g a p p a r a t u s . The p r i m a r y e v e n t s o f p h o t o s y n t h e s i s t a ke p l a c e i n a p h o t o s y n t h e t i c u n i t where a l a r g e number o f c h l o r o p h y l l ( C h i ) m o l e c u l e s a c t c o o p e r a t i v e l y as an antenna t o a b -so rb v i s i b l e l i g h t and t o t r a n s f e r the e l e c t r o n i c e x c i t -a t i o n , so p roduced t o a p h o t o r e a c t i o n c e n t r e or t r a p . ^ In the e x c i t e d t r a p , an e l e c t r o n i s e j e c t e d f rom a s p e c i a l 7 p a i r o f c h l o r o p h y l l m o l e c u l e s , C h i , t h e r e b y c r e a t i n g sp a r a d i c a l , C h l ^ , i n wh i ch t he u n p a i r e d e l e c t r o n i s d e l o c a l i z e d o ve r the n - s y s tems o f b o t h m a c r o c y c l e s . The C h i o f pho to s y s t em I i n g reen p l a n t s {i.e. t h e sp r a d i c a l o f P700) has a c h a r a c t e r i s t i c Gau s s i a n e l e c t r o n s p i n r e sonance (ESR) s i g n a l w i t h a f r e e - e l e c t r o n g - v a l u e o f 2 . 0 0 2 5 and a s i g n a l w i d t h {i.e. t w i c e t he G a u s s i a n • 8 s t a n d a r d d e v i a t i o n ) o f 7 gauss (1 gauss = 10 t e s l a ) . E v i d e n c e f o r t h e p a r t i c i p a t i o n o f j u s t two c h l o r o p h y l l m o l e c u l e s i n s h a r i n g the in vivo u n p a i r e d e l e c t r o n comes o f rom ESR and e l e c t r o n n u c l e a r doub l e r e sonance (ENDOR) s p e c t r o s c o p y . A compa r i s on o f the s i g n a l w i d t h f o r the monomeric C h i r a d i c a l in vitro w i t h t h a t o f P 7 0 0 in vivo - 3 -r a d i c a l shows that the l a t t e r i s reduced r e l a t i v e to the former by a factor of approximately 1 / V 2 . Theory pre-dicts that the signal should be narrowed' by a factor of approximately 1/VN when an unpaired electron i s spread 8 8 equally over N Chl molecules. Both in vivo ESR and q ENDOR evidence supports a two-molecule species for the in vivo P700 r a d i c a l . SCHEMATIC REPRESENTATION OF THE PROPOSED STRUC-TURE OF SPECIAL-PAIR CHLOROPHYLL_a. FOR CLARITY THE GROUPS ATTACHED TO RINGS I AND II ARE NOT SHOWN. R = PHYTYL AND R' IS H, ETHYL, OR PROTEIN, (REF. 55) The primary events in photosynthesis may be viewed schematically a s 1 0 : P 1 C D P 2 + hv > ? 1 n D * ? 2 > * ? l + ' ^ ? 2 where P 1 r e p r e s e n t s the primary electron donor (the f i r s t stable species which has lost an electron after the absorption of a quantum of l i g h t energy), ? 2 i s the primary e l e c t r o n acceptor (the f i r s t s t a b l e s p e c i e s which has gained an e l e c t r o n a f t e r the a b s o r p t i o n of a quantum of l i g h t energy), and the box r e p r e s e n t s the antenna pigments, p r o t e i n and whatever other m a t e r i a l i s neces-sary f o r a f u n c t i o n i n g phototrap. The part of the p r i -mary photochemistry which i s best understood i s the primary e l e c t r o n donor u n i t . In b a c t e r i a l p h o t o s y n t h e s i s , which i s the best c h a r a c t e r i z e d of a l l p h o t o s y n t h e t i c systems, i s a b a c t e r i o c h l o r o p h y 1 1 aggregate which c o n s i s t s of fou r separate but i n t e r a c t i n g molecules s p e c i -al 11-13 f i c a l l y boung by a p r o t e i n . ' When t h i s aggregate i s e x c i t e d , and an e l e c t r o n i s subsequently l o s t , the c a t i o n r a d i c a l thus formed i s apparently shared e q u a l l y 8 14-16 over at l e a s t two of the b a c t e r i o c h l o r o p h y l l molecules. ' This s p i n d e l o c a l i z a t i o n i s probably important i n both s t a b i l i z i n g the o x i d i z e d s p e c i e s and a l s o i n p r o v i d i n g f o r the secondary o x i d a t i o n of cytochrome c^ at some d i s t a n c e from the l o c a t i o n of the reduced primary s p e c i e s , perhaps on the opposite s i d e of the membrane. There are other b i o l o g i c a l systems that a l s o func- .. t i o n through m u l t i p l e p o r p h y r i n c e n t r e s . For example, i t i s assumed that e l e c t r o n t r a n s p o r t r e a c t i o n s from one heme p r o t e i n (eg.; cytochrome oxidase) i n v o l v e a c l o s e approach of i r o n p o r p h y r i n c e n t r e s e i t h e r through a shared l i g a n d or of the po r p h y r i n edges. 17 Heme p r o t e i n p a r t i c i p a t i o n i n oxygen t r a n s p o r t , peroxide r e d u c t i o n and d i s p r o p o r t i o n a t i o n , the mitochond-r i a l e l e c t r o n t r a n s p o r t c h a i n , and drug metabolism ( c y t o -- 5 -chrome P 4 5 0 ) stresses the b i o l o g i c a l importance and d i -verse roles of the iron porphyrins. Iron protoporphyrin IX (heme) i s the prosthetic group of hemoglobin (Hb), myoglobin (Mb), catalase, peroxidase, and many of the c y t o c h r o m e s . The respiratory pigment hemoglobin contains four heme prosthetic groups and i s distributed in red blood c e l l s ; myoglobin i s a monomer found i n muscle c e l l s . Both pigments reversibly bind oxygen for use i n c e l l u l a r catabolism. Hydroperoxidases are hemiproteins (iron i s •3 + present as Fe i n the resting enzyme) which serve to catalyze the reaction 2 H 2 0 2 catalase ^ 2 H 2 0 + 0 2 Q in the case of catalase or a peroxidative reaction ROOH + H2A peroxidase > ROH + H20 + A ^ The reaction pathways by which these enzymes act are complex. C 0 2 H C 0 2 H ( 4 ) - 6 -When nature uses chlorophyll as a source of electrons i t i s not too surprising that i t i s the dihydroporphyrin ring rather than the divalent magnesium ion which sup-p l i e s them. With iron porphyrins, however, i t has gen-e r a l l y been assumed that the iron atom i t s e l f i s the entity which undergoes the redox reaction, and in the cytochromes which function via an Fe (II) Fe(III) couple, there i s no doubt that i t i s the metal which i s 18 the eventual s i t e of electron capture or release. There are two closely related series of iron por-1 Q phyrin containing enzymes, the catalases ^ (Cat) and 20 the peroxidases (which are t y p i f i e d by horseradish peroxidase (HRP)). The re s t i n g enzymes both contain t r i v a l e n t iron and are oxidized by the hydrogen peroxide. The f i r s t intermediate observed spectrophotometrically during t h i s oxidation i s the so-called primary compound (Cat I or HRP I) which has two electrons less than the parent ferrihemoprotein. A one-electron reduction of the green primary compound forms the brown-red secondary compound (Cat II or HRP I I ) . While the f i r s t step i n the c a t a l y t i c cycle of these two enzymes i s the same, i.e.; a two-electron oxidation, by hydrogen peroxide, to t h e i r primary compounds, the two enzymes then perform different functions. Cat I oxidizes a second molecule of hydrogen peroxide to molecular oxygen and i s I t s e l f reduced back-to the ferrihemoproteln, while HRP I reacts with a hydro-gen donor AH 2 to give a free r a d i c a l and the secondary compound of the enzyme HRP II (eq. k) which can in turn o x i d i z e a second donor molecule with the formation of the 18 f e r r i h e m o p r o t e i n (eq. 5 ) . HRP I + AH 2 ^ HRP I I + AH"+H+ HRP II + AH 2 > HRP + AH'+H+ (5) In the I 9 6 I Report of the Commission on Enzymes of the I n t e r n a t i o n a l Union of Bioc h e m i s t r y {cf. a l s o the Enzyme Nomenclature Recommendations, 1965) cytochromes are d e f i n e d as "hemoproteins whose p r i n c i p a l b i o l o g i c a l f u n c t i o n i s e l e c t r o n and/or hydrogen t r a s p o r t by v i r t u e of r e v e r s i b l e valency change of t h e i r heme i r o n " . A d i s -c u s s i o n of t h i s d e f i n i t i o n i s giv e n by Lembert and B a r r e t t . Cytochromes P -450, f i r s t detected i n mammalian micro-somes, are a c l a s s of hemoproteins concerned with enzymic h y d r o x y l a t i o n , demethylation, N - o x i d a t i o n , and p o s s i b l y 22 a l s o the anaerobic r e d u c t i o n of azo and n i t r o compounds. Before h y d r o x y l a t i o n can occur, P - 4 5 0 has the probable m u l t i p l e tasks of s u b s t r a t e r e c o g n i t i o n and b i n d i n g , 23 e l e c t r o n acceptance, then C>2 b i n d i n g and a c t i v a t i o n . During the enzymic c y c l e of cytochrome P-450 f e r r i c c y t o -chrome P-^50 f i r s t combines with a s u b s t r a t e , f o l l o w e d by o n e - e l e c t r o n r e d u c t i o n to form a f e r r o u s cytochrome P - 4 5 0-substrate complex which can bind e i t h e r oxygen or CO r e v e r s i b l y . 2 i | ~ 2 6 I t i s suggested that the " a c t i v a t e d " oxygen, formed a f t e r the a d d i t i o n of the second e l e c t r o n to the O 2~P -450 complex, i n t e r a c t s with the s u b s t r a t e to giv e r i s e to hy d r o x y l a t e d product, water, and f e r r i c cytochrome P -^50 . Thus, cytochrome P-^50 not only func-t i o n s as an e l e c t r o n t r a n s p o r t e r but resembles the oxygen -8-c a r r i e r s hemoglobin and myoglobin, in terms of i t s capa-27 b i l i t y toward 0^ binding. The a x i a l ligands of the heme iron in cytochrome P - 4 5 0 are of great i n t e r e s t , since they hold the key to our understanding of the enzymic function and the under-lying p r i n c i p l e s that enable the single complex protoherie to perform various functions ranging from oxygen transport, oxidation c a t a l y s i s , to electron transport. The possi-b i l i t y of a x i a l sulfur l i g a t i o n in cytochrome F - 4 5 0 has been repeatedly expressed in the l i t e r a t u r e based r-cir 2 6 , 2 8 - 2 9 on E P E evidence. ' Cytochrome c was named and described in the c l a s -s i c a l work of D. K e i l i n ( 1 9 2 5 , 1 9 2 6 ) 3 0 " 3 1 which established i t s wide occurence in c e l l s from mammals to invertebr-ates and yeast. The b i o l o g i c a l role of cytochromes in c e l l u l a r r e s p i r a t i o n was established by K e i l i n (in 1 9 6 6 ) , 3 2 but today we know that i t i s not r e s t r i c t e d to processes of c e l l u l a r r e s p i r a t i o n . Cytochromes c play also an important r o l e in photosynthetic processes and in anaer-obic dark processes of bacteria such as n i t r a t e and sulphate reduction. A short summary of the occurence and of some of the properties of the cytochromes of type c i s given by Lembert and Barrett (see Ref. 2 1 , pp. 1 2 4 -1 2 5 ) . Cytochrome oxidase i s a very important part of the mitochondrial respiratory chain. It i s responsible for both electron transport leading to the reduction of 0 2 33-35 to water, namely -9-0 2 + 4H + + 4e~ >2H 20 (6) and the conservation of the energy required for ATP synthesis.36—38 cytochrome oxidase contains two cop-per ions and two heme groups (a and a^) per subunit. When the reaction with 0 2 is carried out at 25° , the 3 ° measured rates are such that Greenwood and Gibson, conclude that any Intermediates must have h a l f - l i v e s of less than 10/usee. Several mono- and dioxygenases (metalloenzymes), which reduce oxygen with concomitant oxidation of organic substrates, also contain more than one functional metal ion. These include the monooxygen-ases laccase (mono-phenol monooxygenase, 4Cu), and ascor-bate oxidase (8Cu) as well as the dioxygenase L-trypto-phane oxygenase (2 hemes and 2Cu). In contrast to the large number of b i o l o g i c a l systems that reduce 0 2, evolutionary processes appear to have developed only a single dinitrogen f i x i n g system, n i t r c -40 genase. Although the molecular mechanism has not yet been elucidated, a binuclear metal s i t e for dinitrogen 41 reduction has been proposed. (b) Synthetic porphyrin dimers, t h e i r syntheses and the uses to which they have been put.  The study of electron transfer within naturally occuring porphyrin aggregates i s d i f f i c u l t because of the complexity of the systems in which they occur and would be greatly aided i f simple dimeric and polymeric porphyrin molecules were available. - 1 0 -Dolphin et al.; were the f i r s t to report the synthesis of covalently-linked dimeric porphyrins,' joined by amide linkages, CO-NH-R-NH-CO, where R i s either an ethylene or p-phenelene group, as shown ( 5 ) 5 Electronic energy transfer between non-conjugated co-valently-linked chromophores has been demonstrated i n a variety of cases. The problem i s intermediate be-tween studies of electronic relaxation within a single molecule. A covalent linkage has several inherent advantages: (a) The distance between the chromophores o can be known and varied from several to many Angstroms, (b) The orientation of one chromophore with respect to the other may sometimes be r i g i d l y fixed whereas intermolecular energy transfer in solutions involves randomly oriented molecules. (c) Since the energy i s transferred within the molecule, the role of the environ-- l i -me nt i s minimal. In t h e i r study, Dolphin et al.; i n v e s t i g a t e d i n t r a -molecular energy t r a n s f e r i n a s e r i e s o f double porphy-r i n molecules. The two 12,17-diethyl-3,7,8,13,18-penta-methylporphyrin carboxamide molecules ( 5 ) , were s t r u c t u r -a l l y i d e n t i c a l except f o r the metals M and M ' , which were 42 e i t h e r Zn, Cu or Co. Their choice of metals was based on the energy l e v e l s and luminescence c h a r a c t e r i s t i c s . Zn 44 f l u o r e s c e s and phosphoresces, Cu luminescences from the 45 46 t r i p d o u b l e t or q u a r t e t , while Co has no emission. The Cu phosphorescence has a f a r shorter l i f e t i m e than the 47 Zn. 42 Since the f i r s t report by Dolphin et al.; of c o v a l e n t l y - l i n k e d dimeric porphyrins, j o i n e d by amide linkages (5)> a number of s i m i l a r dimeric porphyrins with 48-^7 amide, e s t e r , or ether linkages have been reported. The development of e f f i c i e n t c a t a l y s t s f o r the r e -v e r s i b l e m u l t i e l e c t r o n r e d u c t i o n of 0^ a n d N2 w o u l d have great s i g n i f i c a n c e . Such c a t l y s t s are e s s e n t i a l to the oxygen cathode of an air-powered f u e l c e l l and to e l e c t r o -chemical n i t r o g e n f i x a t i o n . Many monometallic macro-c y c l i c complexes adsorbed on graphite have been examined 58 as c a t a l y s t s f o r oxygen re d u c t i o n . The most e f f e c t i v e macrocycles have four nitrogen donor atoms. In the phthalocyanine s e r i e s ( 6 ) , the order of r e a c t i v i t y i s Fe >Co> Ni>Cu> Mn. However, such stud i e s have f a i l e d to r e v e a l any c a t a l y s t that i s capable of r e v e r s i b l e r e d u c t i o n of 0^ to water, p o s s i b l y because with » s i n g l e - 1 2 -Collman et a l . , have approached t h i s problem, of the development of e f f i c i e n t catalysts for the revers-i b l e multielectron reduction of C>2 and N 2, by construct-ing a new class of so-called "face-to-face porphyrins" in which two porphyrin rings are held i n p a r a l l e l con-formation. Thus, two metal atoms might act i n concert to bind and reduce dioxygen (or dinitrogen) i n the gap between the porphyrin rings. Eventually these binuclear, cyclophane porphyrin complexes are to be attached to graphite to be tested as electrode catalysts. 5 0 Chang et a l . 3 have synthesized three homologous c o f a c i a l diporphyrins (7) that have interplanar distances o o ranging from 6.4A to 4.2A. These c o f a c i a l diporphyrins have great s i g i f i c a n c e in many branches of chemistry. As organic molecules, in addition to being challenging synthetic targets, -13-they may present a multitude of properties by the mere token of th e i r size and the r e s u l t i n g i n t e r a c t i o n of 59 the two Ion-electron porphyrin rings. As inorganic molecules, they have the unusual c a p a b i l i t y of constrain-ing two metal ions at selected distances and thus, may display i n t e r e s t i n g properties a r i s i n g from metal-metal interactions. Furthermore, from the point of view of biochemistry, they represent a class of elaborately designed bioinorganic models for many essential b i o l o g i -cal systems; eg. (a) the cytochrome oxidase model capable of multi-electron reduction of oxygen; (b) the monooxy-genase model by which molecular oxygen can be "activated" via two-electron transfer; (c) polynuclear complexes with certain c a t a l y t i c a c t i v i t y , among these we may c i t e : Mn-Mn dimer for oxidation of water and decomposition of superoxide, Ru-Ru and Mo-Mo dimer for binding and reduction of dinitrogen, also Rh-Rh systems for formation of organometallic compounds (eg. Rh-CH=CK-Rh); (d) the "special p a i r " chlorophyll model i n photosynthetic units; and (e) chlorophyll aggregates model for studying e x c i t -ation energy transfer processes. Appropriate'models are essential to our complete understanding of the mechan-ism of trapping of the absorbed l i g h t energy during the primary photochemistry i n photosynthesis. When i t be-comes possible to reproduce in model systems the high e f f i c i e n c y for converting l i g h t energy into chemical potential that i s exhibited by the in v i v o system, i t may then be possible to construct solar c e l l s of high - I n -e f f i c i e n c y and possibly at low cost. (7) R = -CH 2CH 2COIKN-BU)CH 2CH 2CH 2-, D = 6.^A R = -CH2C0N(N-BU)CH 2CH 2CH2- , D = 5.4A R = -CH 2C0N(N-BU)CH 2CH 2- , D = (REF, 50) A l l the covalently-linked dimeric porphyrins reported so far (see Refs. 4 2 , 4 8 - 5 7 ) , are joined by amide, ester or ether linkages. That a l l of these systems employed the coupling of porphyrins, through these functional groups, re s u l t s from the 'ready' a v a i l a b i l i t y of the porphyrin precursors and the ease of formation of amide, ester and ether linkages. However, once formed, such linkages have numerous disadvantages i n that they gener-a l l y lower the s o l u b i l i t y (<of systems which naturally -15-have low s o l u b i l i t i e s ) , and increase the r e a c t i v i t y and thereby decrease the s t a b i l i t y . In addition the presence of extraneous functional groups complicates mechanistic and spectral studies on such systems. Dolphin and Paine, in our laboratory, recently r e p o r t e d ^ the synthesis of dimer porphyrins ( 8 ) , i\2 4 8-57 Whereas a l l previous syntheses of dimeric porphyrins 5 consist of j o i n i n g two preformed porphyrin e n t i t i e s i n the f i n a l steps, the approach by Dolphin and Paine con-s i s t s of constructing the covalent l i n k f i r s t , and then building a porphyrin onto either end. To avoid the disadvantages of the linkages discussed above, the syn-thesis of dimer porphyrins ( 8 ) has been developed where the hydrocarbon chain plays a passive role both chemically and e l e c t r o n i c a l l y . The various dimeric porphyrins covalently Joined via amide, ester or ether linkages have been studied spectroscopically. The electronic absorption spectra of these various dimers show a variety of changes in -16-in t h e i r electronic t r a n s i t i o n s , compared to the corres-ponding monomeric species, which are related to small changes in t h e i r conformations. Thus a blue s h i f t i n the Soret band of the c o f a c i a l porphyrin dimers has been observed by Chang et a l . ^ ^ and Collman et a l . ^ 5 3 whereas Kagan et al. saw no change i n the Soret region but a considerable red s h i f t in the v i s i b l e region. Dolphin et al. , ^  have studied the interactions between the dimeric porphyrins ( 8 ) using t h e i r electronic 1 3 absorption spectra and C n.m.r. spectra. The ele c t -ronic spectra for the free bases n = 0, 1 and 8 have been compared with those for monomeric etioporphyrin I ( 9 ) , The spectra of the same four species in t h e i r protonated forms (each porphyrin r i n g i s an N,N-diprotonated dication) are also discussed. For the dimer ( 8 ) (n = 8) no changes are observed between i t s spectra, of both the free base and protonated cations, and those of etioporphyrin I ( 9 ) , -17-suggesting that the two porphyrin rings in this dimer o (whose centres could be greater than 15A apart) do not interact. But in the n = 1 and n = 0 dimers, a s i g n i f i -cant effect of the Soret band i s observed, including the appearance of two resolved bands in the dication c a s e . ^ The electronic i n t e r a c t i o n between the two porphyrin rings in the dimers ( 8 ) i s also evident when examining 13 t h e i r C magnetic resonance spectra. The spectra were obtained from deuteriochloroform solutions containing an excess of t r i f l u o r o a c e t i c acid, to increase the s o l u b i l -i t y and allow the observation of a carbons by eliminating NH tautomerization.^ c For chain length ^ 3, the porphyrin nuclei are largely pseudosymmetrical, as the charge-re-pulsion entailed by diprotonation of each macrocycle should tend to minimise the interaction. The meso carbons give only a single broad peak for a l l n g r e a t e r than 2, but resolve into four well-defined peaks for n less than (c) The advantages of the porphyrin dimers we synthe-sized, with respect to the other dimers. Because of t h e i r ease of preparation tetraaryIpor-phyrins have been widely used as models for the naturally occuring p o r p h y r i n s . ^ The reaction between pyrrole and aldehydes repre-sents one of the f i r s t syntheses of meso-substituted 64 porphyrins, and at the present time affords the most convenient route to the large scale preparation of syn-65 t h e t i c porphyrins. In 1939, Rothemund isolated meso-tetraphenylporphyrin (TPP) (10) from a sealed tube re--18-action of pyrrole and benzaldehyde i n pyridine at 150°. It was la t e r f o u n d ^ that the addition of zinc acetate to the reaction improved the y i e l d of porphyrin, and these conditions have been widely used in the prepar-er y ation of a variety of meso-substituted porphyrins. Under these reaction conditions y i e l d s rarely exceed 10%, and the porphyrin i s invariably contaminated with the corresponding c h l o r i n (11), R i - R ^ - H (11) Rl~Rzf-H An examination of the stoichiometry of the reaction shows that the formation of a mole o f TPP, from four moles of pyrrole and four of benzaldehyde, requires six oxi-d i z i n g equivalents. Accordingly the y i e l d of porphyrin increased from 10 to h0% when the Rothemund reaction was carried out In reflux i n g acetic acid, rather than under the anaerobic conditions of the sealed t u b e . ^ D o l p h i n ^ has reported a detailed study o f the mechanism o f the Rothemund reaction and has isolated some reaction i n t e r -mediates i n the synthesis o f meeo-tetraphenyIporphyrins from pyrroles and benzaldehyde. B r i e f l y the formation -19-of meso-substituted porphyrins from pyrroles and benz-69 aldehyde can be summarized as follows: 4 Pyrrole + 4 Benzaldehyde -* Porphyrinogen Q2) + ^Kp0 I Porphomethene (13) i Porphodimethene QH|) Porphyrin QfJ) (13) In t h i s work, we have synthesized meso-tetraphenyl-porphyrin and other meso-substituted tetraarylporphyrins 70 following the procedure developed by Adler et al. The y i e l d and rate of the condensation of pyrrole and benzal-dehyde to TPP have been found to depend on the a c i d i t y , the solvent, the temperature, the a v a i l a b i l i t y of atmos-pheric oxygen, and the i n i t i a l concentration of the rea-68 gents. The procedure where equimolar amounts of pyr-r o l e and benzaldehyde are refluxed i n propionic acid solvent represents the most convenient method for rapidly and reproducibly obtaining a 20 ± 3% y i e l d of c r y s t a l -l i n e TPP of high purity. -20-Th e c e n t r a l r o l e played by o x i d a t i o n / r e d u c t i o n r e a c t i o n s of porphyrins i n photosynthesis and e l e c t r o n transport mechanisms coupled with the well-recognized c r y p t o o l e f i n i c nature of the p e r i p h e r a l double bonds i n 71-7 4 porphyrins has prompted us to i n v e s t i g a t e the d i -imide r e d u c t i o n of the meso-tetraarylporphyrin dimers (15) and (16). The porphyrin dimers 5,10,15-triphenyl-20- [4- [6-(10,15,20-tripheny1-5-porphinyl)-phenoxy]hexoxy] phenyl]porphine (15) and 5 , 1 0 , 1 5 - t r i - p - t o l y l - 2 0 - [ 4 - [ 6 -[p-tolyl-5-porphinyl)-phenoxy]hexoxy]phenyl]porphine (16) were synthesized and c h a r a c t e r i z e d as described i n the Experimental S e c t i o n . -21--22-We have been able to demonstrate that porphyrins and chlorins are indeed readily reduced by diimide produced from the standard diimide precursor p-toluenesulfony1-75 hydrazine and that diimide reduction i s the best syn-t h e t i c procedure for preparing reduced derivatives of the tetraphenyIporphyrin r i n g system. To date no synthetic method has been devised in which the c h l o r i n , and almost any other hydroporphyrin macrocycle, i s b u i l t in the r a t i o n a l step-by-step fashion now commonly employed in porphyrin synthesis. Chlorins are usually found as the 69 7 c undesired by-products in meso-tetraarylporphyrins. ^ The general synthetic approach to chlorins involves f i r s t the synthesis of the respective porphyrin and then i t s subsequent reduction to c h l o r i n . It i s noteworthy that the same approach i s used i n the biosynthesis of chloro-77 p h y l l s , too. A f u l l i nvestigation of the late stages of biosyn-thesis of the chlorophylls has been hindered by the i n s o l u b i l i t y of the intermediates and the relevant enzymes 7 R The pathway was f i r s t outlined by Granick on the basis of the intermediates which accumulate in mutants of C h l o r e l l a v u l g a r i s which are unable to make chlorophyll i t s e l f . Protoporphyrin-IX (17) i s considered to be the last metal-free precursor of chlorophyll-a and bacterio-70 chlorophyll. In green plants, chlorins are generated only i n l i g h t . E t i o l a t e d seedlings accumulate the por-phyrin protochlorophyllide (18), &nd s o the formal t r a n s -hydrogenation of r i n g D, to give chlorophyllide-a (19), - 2 3 -80 could be a photochemical reduction or one switched on by l i g h t . The reaction has been extensively studied and i t i s found that the protochlorophyllide i s bound to a protein forming a so-called holochrome. After the reduction of r i n g D, a l l that remains for the formation of chloro-phyll-a (2) from chlorophyllide-a (19) i s the e s t e r i f i c a -tion of the propionate carboxyl group with the C^Q alcohol phytol (20) 81 (17) C02R C02CH^ (19) (20) The best approach to the etio-type chlorins i s the treatment of porphyrins with reagents t y p i c a l for the hydrogenation of isolated double bonds. Reactions of t h i s type support an el e c t r o n i c structure of the porphyrin macrocycle i n which at least two of the peripheral double bonds do not f u l l y p a r t i c i p a t e with the 18 TT aromatic -24-conjugation system. The behaviour of tetraphenylporph-y r i n QO), tetraphenylchlorln Q l ) , zinc tetraphenyl-porphyrin and zinc tetraphenylchlorln toward p-toluene-sulfonylhydrazine i n pyridine i s summarized i n Scheme I. SCHEME I. Reduction of Tetraphenylporphyrin (TPP), Tetraphenylchlorln (TPC), Zinc TPP (ZnTPP) and Zinc TPC (ZnTPC), with Diimide i n Pyridine.* TPP > TPC > TPBC ZnTPP > ZnTPC » ZnTP-i-BC * TPBC = tetraphenylbacteriochlorin (21), ZnTP-i-BC = zinc tetraphenylisobacteriochlorin (22). (21) R 1-R Z |=H (22) R 1-R Z {=H A remarkable feature of these reductions i s the influence on the course of the reaction of metal-free tetraphenylchlorln Q l ) affords tetraphenylbacteriochlorin (21) contaminated by no more than 2-4£ of tetraphenyliso-b a c t e r i o c h l o r i n (TP-i-BC) as determined by i t s u v - v i s i b l e spectrum. Reduction of zinc tetraphenylchlorln affords -25-the zinc complex of tetraphenylisohacteriochlorin with 8 2 a similar degree of s e l e c t i v i t y . In t h i s thesis, we report the syntheses of zinc complexes of dimeric pophyrin, c h l o r i n and bacte r i o c h l o r i n molecules. We have made the zinc complexes of 5 , 10 ,15-t r i p h e n y l - 2 0 - [4- [ 6 -( 1 0 , 1 5 , 2 0-tripheny 1 - 5-porphiny 1 ) -phenoxy]hexoxy]phenyl]porphine (23) &s well as the chl o r i n (2^1) and bacteriochlorin (25) derivatives. For conveni-ence the covalently linked triphenylporphyrins, c h l o r i n s , and bacteriochlorins discussed in t h i s thesis w i l l be referred to by the following system of nomenclature; TPC-O-C -0-TPC refers to a TPC dimer in which the two chlorins are linked together by an n-carbon a l k y l chain via ether linkages at the para positions of the phenyl groups of the f i r s t and second porphrins. Thus TTP-0-C 6 -0-TTP i s 5 , 1 0 , 1 5-tri-p-tolyl - 2 0 - [ 4 - [ 6 -[p - ( 1 0 , 1 5 , 2 0 -tri-p-tolyl - 5-porphinyl)-phenoxy]hexoxy]phenyl]porhine (16), n (23) - 2 6 -(25) R R R 6 = H - 2 7 -We have synthesized the zinc complexes of dimeric porphyrins (23), chlorins (24) and bacteriochlorins (25) because luminescence properties are well studied in zinc monomers. A discussion of the photochemistry of porphy-rin s and metalloporphyrins i s probably best begun with a consideration of the properties of the excited states involved. It i s generally accepted that the prominent electronic t r a n s i t i o n of porphyrins and the i r metal com-plexes are r m» v* t r a n s i t i o n s associated with the porphyrin ring. Most of the luminescence and photochemistry observed from these compounds i s also associated with the porphyrin 7 T , T T * states even though the life t i m e s and r e a c t i v i t i e s of these states depend strongly on the metal ion incorporated. Although luminescence was early recognized as charac-8^  t e r i s t i c of several porphyrins and t h e i r metal complexes ~ and even used in many cases as an a n a l y t i c a l technique, the f i r s t systematic study of the influence of di f f e r e n t metals on porphyrin fluorescence and phosphorescence was 84 by Becker and Kasha in 1 9 5 5 - A discussion of the emis-sion properties of free base and metallo-porphyrins re-ported to date at room temperature in f l u i d medium and i n l i q u i d nitrogen temperature ( 7 7 ° K ) , i s given by Hopf and 85 Whitten. In general most free base porphyrins, chlorins and related compounds show strong fluorescence at room temperature and both fluorescence and phosphorescence in r i g i d glasses. Metalloporphyrin luminescence f a l l s into several categories, dependent largely on the electronic 8 5 structure of the metal. - 2 8 -Th e other reason we sythesized the zinc complexes (23)i (2 )^ and (25) i s that the redox chemistry of zinc monomeric porphyrins (and the corresponding reduced porphyrins) 8 6 i s well studied. i n 1937, Rabinowitch and Weiss treated chlorophyll-a (2) with f e r r i c chloride, thereby obtaining a chemically oxidized species whose o p t i c a l spectrum was similar to that produced by photooxidation. Although the product was not f u l l y characterized, t h i s reaction i s possibly the e a r l i e s t preparation of a fr-cation r a d i c a l 87 of a porphyrin derivative. In 1957, George et a l . , advanced the suggestion that ir-cation r a d i c a l s were formed by electron abstraction from the porphyrin Tr-system without interruption of the Tr-conj ugation. It was not 8 8 u n t i l 1964 when Closs and Closs isolated and character-» ized the TT-anion and i r-dianion of 5 , 1 0 , 1 5 , 2 0-tetraphenyl-porphinato-Zn (II) (ZnTPP) that the a b i l i t y of the porphy-r i n ir-system to undergo redox reactions was generally Rq appreciated. Felton gives a detailed discussion where attention i s directed toward re v e r s i b l e electron transfer reactions of metalloporphyrins and c i t e s selected exam- • pies in which the oxidized or reduced complexes have been shown to play a biochemical r o l e . In the Experimental Section o f t h i s thesis we report the syntheses of porphyrin, c h l o r i n , and bacteriochlorin dimers because we view them as appropriate models in the study o f the role o f porphyrin aggregates i n both photo-synthetic and metabolic processes. -29-DISCUSSION The synthesis of the mono-substituted porphrlns (26) and (27) w a s accomplished by means of a mixed-aldehyde approach. One equivalent of a substituted aldehyde (p-hydroxybenzaldehyde) and three equivalents of benzaldehyde or p-tolylaldehyde were condensed with four equivalents of pyrrole". The r e s u l t i n g mono-substituted porphyrin c r y s t a l l i z e d from the reaction mixture along with the corresponding tetraarylporphyrin. The two pophyrins along with small amounts of polysubstituted tetraaryIporphyrins } 90 were then separated by "dry-column" chromatography. The separation was f a c i l i t a t e d by the strongly basic nature of the hydroxy substituents. The synthetic pro-cedure used i s a modification of that i n i t i a l l y developed 7 0 by Rothemund and refined by Adler et al. t o s v n t n e s i z e tetrasubstituted porphyrins (26) R1-R3=H (27) R 1-R3=-CH3 - 3 0 -Th e synthetic route used i n the synthesis of porphyrin dimers i s i l l u s t r a t e d i n Scheme II where the syntheses of TPP-0-Cg-O-TPP (15) and TTP-0-Cg-O-TTP (16) are shown. This one-step synthesis of porphyrins gives yields of up to 11%. The reaction of two moles of (26) with one mole of 1,6-ai-tosyloxyhexane gives the porphyrin dimer (15) i n 7 7 ? y i e l d . After work-up the l a t t e r compound i s easily separated from the s t a r t i n g materials by chromatography since i t i s r e l a t i v e l y non-polar. We have also synthesized the porphyrin dimer TTP-0-Cg-O-TTP (16) by coupling two moles of TTP-OH (27) using one mole of 1,6-dibromohexane instead of 1,6-ditosylhexane with s l i g h t l y lower yie l d s ( 1 2 % ) . - 3 1 -SCHEME II (2 MOLES) (A) 1 ^ 6 - D l T O S Y L O X T H m N E /K 2 C O DMF (B) LB-DIBROMOHEXANE^CG^DMF (1 MOLE) - 3 2 -Diimide reduction of the porphyrins (monomers and dimers) has been carried out using p-toluenesulfonyl-hydrazine. There i s one noteworthy feature of the pre-parative aspects of diimide reduction of these t e t r a a r y l -porphyrin derivatives. DDQ dehydrogenation of tetraphenyl-bacterlochlorin i s s u f f i c i e n t l y faster than dehydrogen-ation of the c h l o r i n that the most e f f i c i e n t c h l o r i n pre-paration involves reduction of tetraphenyIporphyrin to a c h l o r i n - b a c t e r i o c h l o r i n mixture followed by addition of DDQ to dehydrogenate the bacteriochlorin. We synthesized TTBC-0-Cg-O-TTBC (28) and TTC-0-Cg-O-TTC (29) with yi e l d s of 65£ and 60% respectively. There are three possible isomers for (29) depending on which of the peripheral double bonds in the two covalently linked macrocycles are reduced. (28) R1"R6""CH3 - 3 3 -Zinc metal i n s e r t i o n into the porphyrins, chlorins and bacteriochlorins was accomplished by the "acetate method". Under the term "acetate method" are those metal-ation reactions where the N-.H protons of the porphyrins (or reduced derivatives) to be metalated are transferred 91 to the acetate ions. A l l metalloporphyrins, metallo-chlorins and metallobacteriochlorins reported i n t h i s study were prepared from reacting the free bases with zinc acetate i n dry pyridine solvent. The conversion to the metallo-derivatives was monitored using v i s i b l e spectroscopy. It should be noted that nearly a l l metallo-chlorins (and metallobacteriochlorins) are unstable with respect to light-induced oxidations by molecular oxygen in some solvents, and some are even unstable i n the s o l i d state. The product of these photooxidations i s seldom a single product such as the corresponding porphine, but usually i s a mixture of the porphine and various compounds - 3 4 -9 2 r e s u l t i n g from cleavage of the r i n g ( s ) . Since the preparative methods given for the metallochlorins and metallobacteriochlorins involve several solvents, i t i s necessary to carry out the preparations (and storage) In the minimum of l i g h t and oxygen. In our study a l l the solvents used for these preparations were deoxygenated by bubbling nitrogen through the solvents for at least half and hour. We attempted to synthesize tetra-meso- [p,p'-(3,3'-phenoxypropoxypheny1 ) ]-strati-iisporphyrin (32). The at-tempted synthesis of stratt-btsporphyrin was approached by 9 3 application of the tetraaldehyde modification-^ of the 70 Adler-Longo porphyrin condensation prodedure. (32) -35-(30) R 1-R Z 4=-0-CH 2CH 2CH 2-BR (31) R 1 -R Z | =-0 -CH 2 CH 2 CH^nLPH -CH0 ,PH=PHENYL Tetra-meso- [p-(3-bromopropoxy)phenyl]porphyrin (30) was synthesized by the reaction of pyrrole with p-3-bromo-propoxybenzaldehyde i n r e f l u x i n g propionic acid. Tetra-meso- [(p'-formyl-3-phenoxy-p-propoxy)phenyl]porphyrin (31) was prepared by reacting (30) with an excess of p-hydroxy-benzaldehyde in dry DMF solvent in the presence of anhyd-rous potassium carbonate. The synthesis of e t r a t i - b i s p o r p h y -r i n (32) w a s unsuccessful following the addition of (31) and pyrrole ( 4 equivalents) to r e f l u x i n g propionic aci d -ethylbenzene (1:1) [0.4mM i n (31)]. We believe that at-tempts to sythesize the e t r a t i - b i e p o r p h y r l n (32) (with a - 3 6 -3 carbon linkage) were unsuccessful because of the s t e r i c s t r a i n a r i s i n g from such a system. We postulate that such a system of co-axial porphyrin rings held together by peripheral linkages, (with 4 carbons or more) could be made. Molecular model studies confirmed t h i s assertion. The proton n.m.r. spectra of compounds prepared in th i s study c l e a r l y indicate the structures of the compounds. Except in the case of TTP-0-Cg-O-TTP (16), the r a t i o of the integrated areas for the peaks i s as expected in a l l cases. I n i t i a l l y , we synthesized (16) because the d i f -ferent chemical s h i f t s of the t o t y l methyls could provide a convenient way of determining stoichiometry via n.m.r. However, It turned out that the r a t i o of the integrated areas corresponding to the t o l y l methyl protons and those of the hexyl protons adjacent to the ether linkages was not as expected. This anomaly arose due to the differences in the spin relaxation times of the two sets of magnetic-a l l y non-equivalent protons, a phenomenon frequently 94 encountered i n F.T. proton n.m.r. spectroscopy. (16) Ri-R6=-CH3 -37-Th e rapid development of proton nuclear magnetic resonance (n.m.r.) spectroscopy since about i 9 6 0 has had a strong influence on the study of almost a l l classes of organic compounds. There are, however, few categories of compounds for which such a wealth of information can be obtained by n.m.r. as for porphyrins. This circum-stance arises for the most part from the large magnetic anisotropy (ring current) of the aromatic macrocycle of these compounds. The rin g current functions as a b u i l t - i n chemical s h i f t reagent, and spreads the proton n.m.r. spectrum of porphyrins over the unusually large range 95 of more than 15 p.p.m. This in consequence generally s i m p l i f i e s interpretation and assignment, and makes pro-ton n.m.r. a very sensitive probe of st r u c t u r a l modifica-tions. The rin g current e f f e c t s , i n addition, allow detailed studies of molecular interactions in solution. The proton n.m.r. spectra of porphyrins, especially some of the metalloporphyrins, are strongly solvent, con-95 centration and temperature dependent. This i s due to the tendency of porphyrins to experience self-aggregation, and t h i s , i n combination with the strong magnetic'aniso-tropy of the porphyrins has major consequences for the proton n.m.r. spectra. In the free porphyrin bases, ag-gregation i s weak, and p a r a l l e l s the T T - T T aggregation be-96 haviour generally observed in aromatic molecules. Under aggregating conditions the accurate determination and assignment of chemical s h i f t s becomes espe c i a l l y important, as aggregation s h i f t s of more than 2 p.p.m. may occur - 3 8 -for the resonances of p a r t i c u l a r protons as a result of close proximity to the r i n g current of another macrocycle. rigorous approach to the problems proposed by aggregation requires mapping the concentration-dependence of the chemical s h i f t s and extrapolation to i n f i n i t e d i l u t i o n , but t h i s procedure i s r e a l l y p r a c t i c a l only for certain important compounds. The aggregation problem in the assign ment of chemical s h i f t s can in general be circumvented by recording the spectra in t r i f l u o r o a c e t i c acid (TFA), in which both T T - T T and coordination-aggregates are broken down by dication formation or by p r e f e r e n t i a l l i g a t i o n of the metal a x i a l coordination s i t e s with TFA. For suf-f i c i e n t l y stable compounds th i s i s a very useful approach, p a r t i c u l a r l y because TFA i s an excellent solvent even for otherwise only poorly soluble free base pophyrins. meso-Tetraphenylporphyrin (TPF) QQ) i s the parent of a variety of compounds not related s t r u c t u r a l l y to the naturally-occuring porphyrins. The proton n.m.r. spectrum m e s o - t e t r a p h e n y I p o r p h y r i n shows two resonances (g-pyrrole H,N-H) for the macrocyclic protons, and two signals for the three phenyl protons well separated from the f i r s t two. Due to s t e r i c hindrance, the phenyl rings in TPP are out of the plane of the macrocycle, they do not ro-tate f r e e l y , and mesomeric interactions between the four ' phenyl groups and the macrocycle are e f f i c i e n t l y reduced. The very si m i l a r chemical s h i f t s for the m - and p-protons of the phenyl groups can be explained on thi s basis. A l -though the ^ -protons are closer to-the macrocycle, they are - 3 9 -out of i t s plane, and thus positioned in a less deshielded region. The N-H tautomerism i s rapid at ambient temperature on the proton n.m.r. time scale, but has been studied 97 at low temperatures. As in proton n.m.r. spectra of porphyrins, the spectra of the chlorins and bacteriochlorins are dominated by the 9 5 ring-current-induced s h i f t s (RIS) of the aromatic macro-cycle. In chlorins and bacteriochlorins one or two of the macrocycle peripheral double bonds are reduced without loss of the macrocyclic r i n g current. Removal of one of the peripheral double bonds leads to a decrease in the r i n g current, as indicated by the up f i e l d s h i f t of the p e r i -pheral proton signals and a downfield s h i f t of the N-H signals. The decrease i s moderate i n chlorins and bacterio-c h l o r i n s , but very pronounced i n isobacteriochlorins (33). In the l a t t e r compounds, the two N-H protons are for the most part located at the two neighbouring (non-reduced) pyrrole rings, a structure which i s unfavourable for a large ring current for both s t e r i c and electronic reasons. (33) -HO-Quantities of materials available in natural product chemistry are often minute, and the technique of mass spectrometry has the advantage that, using only dimunitive samples, i t can provide accurate information, not only -on molecular weights and elemental compositions of com-pounds, but also d e t a i l s of the nature of some of the functions within complex molecules. Both of these factors are of obvious u t i l i t y in s t r u c t u r a l investigations of porphyrins and metalloporphyrins. The major breakthrough in porphyrin mass spectrometry came about 1964 with the introduction of 'direct' insertion probes; before that time i t had been v i r t u a l l y impossible to measure the spectra of i n v o l a t i l e substances, though using extreme measures, some macrocycles had been examined.'' The physical appearance of the molecular ion enables one to ascertain the presence of halogens, metals, etc. in compounds. This i s of great help in i d e n t i f i c a t i o n of unknown metalloporphyrins because of the general tendency for. metal ions not to be lo s t i n fragmentation processes and because the precise isotopic compositions of metals are known. Metal-free porphyrin mass spectra almost i n -variably possess a cluster of peaks to higher mass than the molecular ion. The explanation of the high mass peaks is that there i s scavenging of metal ions by the porphyrin in the source of the spectrometer; i t may even be that each instrument has a 'fingerprint' of metal ions which i s unique, depending upon the parameters and the construc-ti o n of the io n i z a t i o n source. In the examples we studied -41-the metal Ions scavenged were copper Ions. A c h a r a c t e r i s t i c feature of the mass spectra of porphyrinic compounds i s the way in which the ions are s p l i t into at least two separate groups. The highest mass group contains the molecular ion and i t s fragmentation products. After a r e l a t i v e l y bare region the doubly charged series of ions i s observed. Below about - 200 there are e several peaks, in a l l the cases we studied, in d i c a t i n g that there i s extensive cleavage of the macrocyclic nucleus. In organic mass specrometry, a major driving force and s t a b i l i z i n g effect for fragmentation i s usually 99 the formation of even-electron ions. This p r i n c i p l e holds firm In the mass spectra of porphyrinic compounds for both the singly and doubly charged ions, the s t a b i l -i t y difference between even and odd electron ions i s even accentuated by the macro-ring. 1 0 0 Features of the spectra of the tetraaryIporphyrins we studied are well in accord with the s t a b i l i t y of the aromatic nucleus, which allows wide d e r e a l i z a t i o n of the po s i t i v e charges. Metal complexes of porphyrins undergo fragmentation in a sim i l a r manner to the free bases, the only difference being in the physical appearance of ions owing to the isotopic compositions of the metals. Except- in very unusual cases, the metal atom Is not lost In any fragmentation process, and t h i s might be expected because of the sta-b i l i t y of the macrocyclic nucleus towards c l e a v a g e . 1 0 1 Most ch l o r i n mass spectra are broadly similar to those of t h e i r porphyrin counterparts, 'benzylic' cleavages predominating. Thus, the whole substituent i s usally -42-l o s t from the reduced r l n g . ^ 0 ' 1 " mes^-Tetra.pheny I c h l o r i n (TPC) (11) g i v e s a mass spectrum which corresponds to that of the p o r p h y r i n analogue (10), t h i s novel dehydrogenation i s due to e l e c t r o n - i m p a c t e x c i t a t i o n and not thermal • 102 e f f e c t s i n the source of the spectrometer. In almost a l l the dimers we s t u d i e d there was str o n g evidence f o r the cleavage of the ether l i n k a g e s l e a d i n g to the observ-a t i o n of ions such as TPP-OH*, TPC-O* etc; and s i m i l a r ions corresponding to the z i n c m e t a l l o - d e r i v a t i v e s . For a d e t a i l e d d i s c u s s i o n on mass spectrometry of porphyrins and m e t a l l o p o r p h y r i n s the i n t e r e s t e d reader i s advised 101 to see the review by Smith. E l e c t r o n i c a b s o r p t i o n spectroscopy can be used to e l u c i d a t e the gross s t r u c t u r e of porphyrins and t h e i r d e r i v a t i v e s , such as whether the nucleus i s reduced (as i n c h l o r i n s and b a c t e r i o c h l o r i n s ) or whether c e r t a i n metal are c h e l a t e d i n the macrocycle. In 1883, an in t e n s e a b s o r p t i o n band at about 400 nm w 103 d i s c o v e r e d i n hemoglobin by Soret; t h i s was l a t e r ob-10 4 served i n por p h y r i n s by Gamgee. T h i s "Soret" band i s the most i n t e n s e band i n the po r p h y r i n s and t h e i r d e r i v -a t i v e s , molar e x t i n c t i o n c o e f f i c i e n t s , c, around 400,000 o f t e n being recorded. The Soret band i s the band of choic f o r s p e c t r o p h o t o m e t r y d e t e r m i n a t i o n s ; commercial samples of p o r p h y r i n s o f t e n have t h e i r p u r i t y expressed i n terms of the e x t i n c t i o n c o e f f i c i e n t of the Soret band. The u l t r a v i o l e t and v i s i b l e a b s o r p t i o n spectre of t e t r a p h e n y l p o r p h y r i n (10), i t s p-methyl and methoxy de--H3-10 5 r i v a t i v e s i n benzene have been reported. ^ The spectra have been divided i n t o two groups, the f i r s t i n the region of 700 to about 450 nm, and the second from 450 to 350 nm. The absorption bands i n the 700-450 nm-region can be r e -garded as v i b r a t i o n a l terms of a common e l e c t r o n i c t r a n s i -105 t i o n , while the intense band i n the near u l t r a v i o l e t r e g i o n , the s o - c a l l e d "Soret" band, i s found In a l l t e t r a -p y r r o l e s i n which the nucleus i s f u l l y conjugated and can th e r e f o r e be regarded as a c h a r a c t e r i s t i c of t h i s macro-c y c l i c conjugation. Many of the absorption bands of the pa r a - s u b s t i t u t e d d e r i v a t i v e s e x h i b i t small s h i f t s to longer-wavelengths as compared to the e t i o - t y p e spectrum of tetraphenyIporphyrin TPP (10) > (see O p t i c a l S p e c t r a l Ap-l n 5 pendix), while other bands showed no change i n p o s i t i o n . The i n t e n s i t y of the Soret band i s weaker i n c h l o r i n s and m e t a l l o c h l o r i n s . U l t r a v i o l e t - v i s i b l e spectroscopy i s by f a r the most widely a p p l i e d spectroscopic method i n hydroporphyrin ( c h l o r i n s and b a c t e r i o c h l o r i n s ) chemistry and biochemistry. Due to the c h a r a c t e r i s t i c and intense absorptions of many hydroporphyrins and the large number of known s p e c t r a , the method i s s e n s i t i v e and s e l e c t i v e . Considerable e f f o r t has a l s o gone i n a t h e o r e t i c a l i n t e r p r e t a t i o n of the uv-vis spectra of hydroporphyrins. Among the hydroporphyrins, the c h l o r i n s and bac-t e r i o c h l o r i n s as w e l l as t h e i r metal complexes, have c h a r a c t e r i s t i c absorption bands i n the ranges between 350 and 450 nm (Soret or B-band), and 600-900 nm (red or -44-Q-band). In these cases, the assignment of a c e r t a i n chromophoric system by uv-vis measurements i s r e l a t i v e l y safe even i n r e a c t i o n mixtures and b i o l o g i c a l systems. I t should be noted t h a t , i n most hydrop'orphyrins, the i n t e n s i t y of the "Soret" band i s no longer an order of magnitude greater than the red band(s), but, r a t h e r , of comparable i n t e n s i t y . This i s c e r t a i n l y due to the r e -duced symmetry i n the hydroporphyrins and i s e s p e c i a l l y 106 pronounced f o r unsymmetric s u b s t i t u t i o n . C h l o r i n s have an intense narrow red band around 660 nm (CR:70 , 0 0 0 ) , and a Soret band of about t h r e e f o l d i n t e n s i t y around 400 nm. A double band i n the region of 500 nm (e« 15 ,000) i s t y p i c a l f o r free-base c h l o r i n s . Upon m e t a l a t i o n , the disappearance of t h i s band i s the most c h a r a c t e r i s t i c s p e c t r a l change. The red band of m e t a l l o c h l o r i n s i s increased i n i n t e n s i t y , and i n c r e a s -i n g l y b l u e - s h i f t e d with i n c r e a s i n g e l e c t r o n e g a t i v i t y of the c e n t r a l metal. B a c t e r i o c h l o r i n s have a narrow absorption (e« 8 o , 0 0 0 ) at about 750 nm, a s p l i t Soret band, and an absorption of intermediate i n t e n s i t y at about 5^0 nm. As compared to the f r e e bases, the spectra of the metal complexes are r e d - s h i f t e d . ^ 0 ^ As i n c h l o r i n s , the i n t e n s i t y of the red band increases and that of the Soret band decreases upon metalations. The uv-vis spectra of i s o b a c t e r i o c h l o r i n s are i n the red r e g i o n s i m i l a r to those of the c h l o r i n s , but b l u e - s h i f t e d by about 30 nm f o r s i m i l a r l y s u b s t i t u t e d compounds. The Soret band of i s o b a c t e r i o c h l o r i n s i s - 4 5 -s p l i t as in bacteriochlorins. Elemental analyses were performed _on p u r i f i e d com-pounds. The molar r a t i o s C:H:N and the percentages of C,H and N were consistent with the assigned structures. The tetraarylporphyrins we prepared had melting points greater than 3 6 0 ° . The melting point of tetraphenyIpor-107 phine was reported as 4 5 0 ° by Rothemund. Generally porphyrins have very high melting points, Dolphin et a l . ; in their'syntheses of porphyrin dimers, covalently linked v i a amide groups, frequently reported melting points -46-CONCLUSIQNS Singlet energy transfer i s known to occur between chlorophyll, Chi, m o l e c u l e s . ' P r e s u m a b l y the Chi molecules are arranged in planar, p a r a l l e l arrays i n the c h l o r o p l a s t s 1 1 0 in order to f a c i l i t a t e energy transfer. It was therefore of interest to examine the absorption spectra of the porphyrin and metallopdrphyrin dimers (as well as the corresponding hydroporphyrins) prepared In this study. The data in the Experimental Section show that the v i s i b l e absorption bands have positions which are e s s e n t i a l l y i d e n t i c a l to those of the corresponding monomers. The i n t e n s i t i e s are those that would be expected for a molecule containing two non-interacting molecules. In the Soret region the i n t e n s i t i e s of the dimers are as expected. There i s no s p l i t t i n g of the 420 nm bands into two or more components. A s p l i t t i n g of the Soret absorption has been reported by Leonard and Longo. 1 1 1 The authors reported the r e s u l t s of a study of matrix-isolated tetraphenylporphines (TPP) in matrices of n-octane, argon and sulfur hexafluoride. For TPP i n octane with mole r a t i o s less than 500:1 they observed a red s h i f t as the concentration of TPP increases, TPP-TPP interactions become stronger and cause the red s h i f t , as observed in the thin f i l m spectrum. Two bands i n the Soret region of the TPP and TPC matrix-isolated spectra, at about 420 and 400 nm, were observed in both cases. In 112 a previous study, Leonard and Longo had observed a s p l i t t i n g of the Soret absorption of matrix-Isolated porphine. - 4 7 -They had concluded that the porphine was trapped as pairs or "dimers" in the matrix and that the s p l i t t i n g was due to Davydov s p l i t t i n g of molecular states_in pairs. The theory of spectral s h i f t s and s p l i t t i n g of the Soret absorption i s quite complicated. Leonard and Longo 1 - 1 - - 1 - > 1 1 2 have made pair p o t e n t i a l calculations which correlate with the observed experimental r e s u l t s . The absorption spectrum of matrix-isolated porphine shows a greater s p l i t -t ing of the Soret absorption than that of TPP. In the case of TPP and i t s metal derivatives, the bulky phenyl groups are appreciably twisted with respect to the porphine plane and make guest-host interactions much more s i g n i f i c a n t . Thus, less p a i r i n g occurs as compared to the porphine case where there are no bulky phenyl groups. Theoretical calculations of the Davydov s p l i t t i n g were m a d e 1 1 1 3 2 and are, q u a l i t a t i v e l y , in agreement with the observed matrix-isolated spectra for the porphine and TPP cases. Gouterman et a l . j 1 1 ^ have observed a similar temperature dependent s p l i t t i n g of the Soret band i n u-oxometalloporphy-r i n dimers. 42 4 8 - 5 7 The electronic absorption spectra of the various dimers ' show a variety of changes i n t h e i r electronic t r a n s i t i o n s . 4? Dolphin et a l . , i n th e i r study of covalently linked octaalkyIporphyrins did not study free-base dimers. Instead, they prepared mixed metalloporphyrin dimers. The compounds did not show a s p l i t t i n g of the Soret band. Little,'*''' has recently reported the synthesis of covalently linked tetraarylporphyrin dimers that did show a s p l i t t i n g of the Soret band. -48-Th e covalently linked tetraaryIporphyrins we prepared did not show a s p l i t t i n g of the Soret band. Our re s u l t s may be compared to those of Dolphin et al. ^  For t h e i r dimer (8) (n=8) no changes were observed between i t s spectra, of both the free base and protonated cations; and those of the corresponding monomer, suggesting that the two porphyrin rings in t h i s dimer (whose centres could be greater than 15A apart) do hot int e r a c t . The electronic i n t e r a c t i o n between the two porphyrin rings in the dimers can be studied by examining t h e i r proton magnetic resonance spectra. The chemical s h i f t s for the t o l y l methyls of 5-(4-hydroxypheny1)-l0,15,20-t r i t o l y Iporphyrin (TTP-0K) (27) were found to be 6 = 2.68 p.p.m. while those for the dimer TTP-O-Cg-O-TTP (16) were between the ranges 6 = 2.63-2.65 p.p.m., in other words, the t o l y l methyls of the monomer (27) & r e more shielded than those of the dimer -(16)- Examination of the proton magnetic resonance spectra shows that the chemi-cal s h i f t s for the pyrrole N-H protons of the porphyrin monomers,eg. TPP, are e s s e n t i a l l y the same as those of the corresponding dimers. Thus as would be expected by considering the s t e r i c r e s t r a i n t s for the dimer molecules which were constructed with a long (6-carbon) linkage, there i s no evidence from the n.m.r. for porphyrin-porphyrin inte r a c t i o n due to the molecule folding back on i t s e l f . In contrast to the generally straightforward interpretation of proton magnetic resonance (p.m.r.) spectra in porphyrins the p.m.r. spectra of chlorins and bacteriochlorins are - 4 9 -often very complex. One reason Is the reduced r i n g cur-rent s h i f t s . An additional complicating factor i n these compounds i s the p o s s i b i l i t y of long-range spin-spin coup-l i n g of the protons on the reduced ring(s) with the pyr-95 role N-H. Due to the complicated p.m.r. spectra for the dimeric chlorins and bacteriochlorins, there i s no cl e a r -cut evidence for c h l o r i n - c h l o r i n or bacteriochlorin-bac-t e r i o c h l o r i n i n t e r a c t i o n due to the molecule(s) fo l d i n g back on themselves. There are other experiments that could be done to increase porphyrin-porphyrin i n t e r a c t i o n in the dimers. We could have done low temperature experiments similar to those of Leonard and Longo"'""''~1',in which they studied matrix-isolated porphyrins. Our compounds have a good deal of conformational freedom and thi s apparently leads to a decrease in porphyrin-porphyrin interaction. Our singly-linked metalloporphyrin dimers, perhaps, could be constrained to a face-to-face conformation using chelating ligands. Thus, a suitable a x i a l ligand bridge between the two zinc ions could be found that could bring about the required face-to-face conformation. Tsutsui and 114 Taylor discuss some a x i a l ligand bridges in model com-pounds that can be considered relevant to the cytochrome oxidase system. Among them we may c i t e the azide, oxygen, halide and imidazolate bridging species. EXPERIMENTAL Electronic spectroscopy V i s i b l e spectra were obtained on a Cary 17 recording spectrophotometer. Dichloromethane spectro-grade was used as solvent, unless otherwise s p e c i f i e d . U n i t s f o r t h e molar e x t i n c t i o n coeffient,£,are mol~\im \ Nuclear Magnetic Resonance Nuclear magnetic resonance Fourier-transform spectra were taken at either 100 MHz or 270 MHz with a Varian XL-100 or Nicolet Model NIC-80 spectrometer. Deuteriochloroform (CDCl^) was the solvent used. Resonances are quoted on the delta, 6, scale r e l a t i v e to tetramethylsilane (TMS) (6=0). Mass Spectroscopy Mass spectra were recorded i n an Atlas CH-4 spectrometer or an A.E.I. MS-902 spectrometer. Melting Point Determination Melting points were measured with a Thomas-Hoover c a p i l l a r y melting point apparatus and are uncorrected. Analysis Elemental analysis for carbon, hydrogen and nitrogen were determined by Mr. P. Borda of the MIcroanalytical Laboratory, U.B.C. Chromatography The chromatographic separations were effected by the "dry column" procedure;^ 0 using either alumina (Fisher S c i e n t i f i c -51-A-540 or A - 9 5 0 ) or s i l i c a gel (.W/oelm-Activity I) purchased from the ICN Pharmaceuticals, Inc. Thin-layer chromatography (TLC) was performed using S i l i c a Gel GF precoated plates (Analtech-Uniplate, 250y). CHEMICALS A l l chemicals were reagent grade unless otherwise spec i f i e d . Pyridine Dry pyridine was obtained by re f l u x i n g reagent grade pyridine over barium oxide for four days and then d i s t i l -l i n g the solvent from the drying agent. DMF Dry DMF was obtained by ref l u x i n g reagent grade DMF over anhydrous CuSO^, and d i s t i l l i n g under reduced pressure. The chromatographic column was f i l l e d 5 w i t h d r y adsorbent (alumina or s i l i c a g e l ) . The m a t e r i a l t o be chromatographed was d i s s o l v e d i n a minimum amount o f so l v e n t and then a p p l i e d on top o f the column. The l e s s p o l a r f r a c t i o n was e i u t e d from the column u s i n g l e s s p o l a r solvent,, The s o l v e n t system was made more p o l a r i n order t o e l u t e the more p o l a r i f r a c t i o n s e I n a l l cases the solvent was a p p l i e d on top o f the "dry column and solvent added u n t i l the product was e l u t e d from the columns -52-PART (A) - SUBSTITUTED TETRAPHENYLPORPHINES  - (MONOMERS AND PIKERS) Synthesis of mgso-Tetraphenylporphin (Compound la) *4 R1 - R 1 4 = H Freshly d i s t i l l e d pyrrole (8 ml, 0.1 mole) and 10 ml ( 0 . 1 mole) reagent grade benzaldehyde were added to 300 ml ref l u x i n g reagent grade propionic acid. After r e f l u x i n g for h a l f an hour the solution was cooled to room temper-ature and f i l t e r e d . The f i l t e r cake was washed with propionic acid, hot water and f i n a l l y with methanol. The puplish c r y s t a l s were a i r dried. The y i e l d of the meso-tetraphenylporphin (TPP) was 2.5g (16% y i e l d ) . The TPP was r e c r y s t a l l i z e d from methylene chloride and methanol to give 1.8g of purple needles. -53-Absorption Characteristics of TPP (Dichloromethane) (Pyridine) Amax, run e x 1 0 " 3 Amax', nm £ X 10 6 4 7 3.3 647 3.9 5 9 2 5.3 5 9 2 5.4 5 4 8 8.0 5 5 0 8.6 5 1 5 18.6 51 5 1 8 . 7 48 5 3.4 4 8 5 3.8 41 9 4 7 8 420 468 - 3 L i t . J Xmax, nm (e x 1 0 ~ 3 ) (Benzene) 4 2 0 ( 4 5 0 ) 4 8 4 ( 5 . 0 ) 5 1 6 ( 2 0 . 7 ) 5 5 0 ( 8 . 5 ) 5 9 2(5.8) 6 4 6 ( 3 - 8 ) M.p. > 3 6 0 ° , L i t . 1 0 7 4 5 0 ° Synthesis of weso-Tetratolylporphin (TTP) (Compound lb) R1-Ki|=-CH Freshly d i s t i l l e d pyrrole (6.7g, 0.1 mole) and 12.Og ( 0 . 1 mole) p-tolualdehyde were added to 300 ml re f l u x i n g - 5 4 -reagent grade p r o p i o n i c a c i d . The r e a c t i o n mixture was re f l u x e d f o r 30 minutes, cooled to room temperature and 70 f i l t e r e d . The procedure adopted was that of Adler et al. No attempt was made to remove the m e e o - t e t r a t o l y l c h l o r i n (TTC) imp u r i t y . The crude porphin was then r e c r y s t a l l i s e d from methylene c h l o r i d e and methanol t o y i e l d 2.4g of purple needles (l4£ y i e l d ) . NMR Data (CDClg) Delta, pprn jf H J, Hz 2.68 12, methyl (s) 7.82 8, t o l y l - 2 , 6 - ( d ) 7.1 8.35 8, t o l y l - 3 , 5 - ( d ) ' 7.1 8 .63 8, e-pyrrole (s) Absorption Characteristics of TTF (Dichloromethane) Xmax, nm 650 592 550 516 485 420 e x 10" 3 4.0 5.4 8.1 18.8 3-6 490 L i t . 1 1 5 (Benzene) Xmax, nm 649 594 551 516 483 420 e x 10" 3 5.8 6.9 12.1 23.0 6.0 558 - 5 5 -Synthesis of 5 - ( 4-Hydroxyphenyl ) - 1 0 , 1 5 , 2 0-trltoIylporphyrin  M.W. 672.8 (Compound Ha) para-Hydroxybenzaldehyde ( 4 . 6 g , 0.038 mole) and 13.5g (0.112 mole) of para-tolualdehyde were mixed with 500 ml of hot propionic acid. Pyrrole ( 1 0 .Ig, 0.15 mole) was ad-ded and the reaction mixture refluxed for one hour. The reaction mixture was cooled, f i l t e r e d and the purple cry s t a l s washed with methanol. The y i e l d of the crude porphyrins was 4 .3g . Thin-layer chromatography (Tic) showed the presence of meec-tetratolylporphin (R^ » 1) and the mono-substituted porphin (R f 0 . 3 ) . There were traces of the d i - , t r i - , and tetra-substituted porphins. The crude porphyrins were dissolved i n 750 ml of methylene chloride and chro-matographed on a 60 x 5 cm column of alumina using methylene chloride as the eluant. The chromatographic separations 90 were effected using the dry column procedure. The f i r s t band eluted from the column was TTP. It was followed by OH - 5 6 -a green band of c h l o r i n impurity. A t h i r d band which moved very slowly was spread out over the top 15 cm of the column. This band was eluted with 1 : 1 : 1 0 methanol-ethy1 acetate-methylene chloride and then taken to dryness under vacuum on a rotary evaporator. This material was redissolved in reagent grade methylene chloride and chromatographed on a 40 x 2 cm column of s i l i c a gel using methylene chloride as the eluant. The elution pattern i s similar to that of the alumina column except that a dark brown band st i c k s at the top of the column and a second band separates slowly from the t a i l of the main porphyrin band. The y i e l d was 1.5s ( 5 . 9 S ) . Mass Spectral Data M/e I M/e I 672 100 (parent) • . 505 9 655 11 455 13 605 12 405 16 5 5 5 12 343 27 336 32 (m/2e) 331 30 NMR Data (CDCl^) Delta, ppm # H J,Hz 2.68 9,methyl (s) 7.48 6, t o l y l - 3 , 5 - ( d ) 8 . 0 8 . 0 5 6, t o l y l - 2 , 6 - ( d ) 8 . 0 8 . 8 3 8 , B-pyrrole (s) - 5 7 -Synthesis of 5 -(4-Hydroxyphenyl ) - 1 0 , 1 5 , 2 0-triphenyIporphyrin (M.W. 630)-(Compound l i b ) The procedure followed was b a s i c a l l y the same as that described for 5-(4-hydroxyphenyl)-10,15>20-tritoly1-116 porphyrin. 6.1g (0.05 mole) para-Hydroxybenzaldehyde and 17.5g benzaldehyde (0.17 mole) were used. Pyrrole (14.7g, 0.22 mole) was then added to the reaction mixture. The reaction mixture was cooled and a l l the propionic acid solvent removed using a rotary evaporator to leave a tarry residue. The residue was redissolved in b o i l i n g methanol and then stood at -10°C overnight. The next day the crude porphyrins were f i l t e r e d and washed several times with methanol, and then a i r dried to give 4.3g of shiny purple c r y s t a l s . The chromatographic separations were effected as on described before. After r e c r y s t a l l i s a t i o n from methylene chloride-ethanol, 0 . 6 g ( 7 . 6 ? ) of the mono-hydroxyporphin was obtained. -58-E m p i r i c a l formula: C^N^H^QO M.W. = 630.76 Calc. Found D i f f e r e n c e c 83-79 83.86 +0. 07 H 4.79 4. 52 -0 . 27 N 8.88 8.95 +0.07 0 2.54 _ P r e p a r a t i o n of 1,6-Ditosyloxyhexane. (Compound I I I ) A s o l u t i o n of 5.0g (0.04 mole) 1,6-hexanediol i n 60ml dry p y r i d i n e i n a 125 ml glass-stoppered Erlenmeyer was cooled to 0°C and tr e a t e d w i t h 33-6g (1 molar excess) of 117 t o s y l c h l o r i d e . Dry p y r i d i n e was obtained by r e f l u x i n g reagent grade p y r i d i n e over barium oxide f o r four days and then d i s t i l l i n g the solvent from the d r y i n g agent. The Erlenmeyer f l a s k was placed i n a r e f r i g e r a t o r f o r 24 hours. The r e a c t i o n can be followed by the development of a yellow c o l o u r , followed by sepa r a t i o n of p y r i d i n e hydrochloride as long needles. When the r e a c t i o n was judged complete, the e n t i r e mixture was poured with s t i r r i n g i n t o 40 of i c e and water. The t o s y l a t e c r y s t a l l i s e d a f t e r 15 minutes a d d i t i o n a l s t i r r i n g . The product was f i l t e r e d , washed wi t h water, d r i e d in vacuo at room temperature. For p u r i f i c a t i o n , the t o s y l a t e was d i s s o l v e d i n a minimum qu a n t i t y of methylene chloride-petroleum ether (30°-60°) at room temperature. A f t e r s t i r r i n g w i t h N o r i t , - 5 9 -the mixture was f i l t e r e d through f i l t e r aid (Celite) and washed. The clean, colourless solution was cooled slowly to -75° in a dry ice-acetone bath with scratching to induce c r y s t a l l i s a t i o n and to avoid o i l i n g out. The cooling to - 7 5 ° was completed and the p r e c i p i t a t e f i l t e r e d . The pre c i p i t a t e was not sucked completely dry but rather transferred to a v i a l for drying in vacuo at room tempera-ture. The ditosylate came out as white needle-like c r y s t a l s . Yield 7 .Ig (39%). M.p. 7 1 ° - 7 2 ° . NMR Data (CDC1,) Delta, ppm § H J,Hz 1.26 4, h e x y l - 3 , 4 - ( t t ) 1.59 4, hexyl - 2 , 5-(t) 2.45 6, methyl (s) 3.99 4, h e x y l - l , 6 - ( t ) 7.35 4, t o l y l - 3 , 5 - ( d ) 8.8 7.79 4, t o l y l - 2 , 6 - ( d ) 8.8 Mass Spectral Data M/e I M/e I 426 100 (parent) 171 32 344 13 155 99 326 17 154 57 2 5 5 68 109 1^ 213 34 (m/2e) 108 60 190 24 - 6 0 -Preparatlon of 1 ,6-Bjs-para-Tormylphenoxyhexane (Compound IV) Sodium hydride suspension i n o i l was washed with an-hydrous ether u n t i l i t was free of the ' o i l . p-Hydroxy-benzaldehyde (16.2g, 2 fold excess) was dissolved i n dry, reagent grade DMF (40 ml). Sodium hydride (6.4g, 0.26 mole) was then added. The reaction mixture was gently warmed u n t i l the evolution of hydrogen was complete, and then cooled. oXy 1,6-DitosyIhexane (13-2g, 0.03 mole) was then adoed A to the reaction mixture. The reaction was allowed to pro-ceed with s t i r r i n g , at room temperature, for 24 hours. The following day, the whole reaction was poured into a 1 l i t r e separatory funnel. Methylene chloride (400ml) was added, and the mixture extracted twice with 150 ml portions of 10* sodium hydroxide solution to remove excess p-hydroxybenzaldehyde. The methylene chloride extract was washed twice with 3N hydrochloric acid to remove the DMF, and f i n a l l y washed with water. It was dried over a mixture of anhydrous potassium carbonate and sodium sulphate. On removing a l l methylene chloride solvent an off-white residue was l e f t behind. The material was r e c r y s t a l l i s e d from ethyl ether-hexane to give 5-5g (54A ) off-white chunky c r y s t a l s . M.p. 93 0-94°. - 6 1 -NMR Data (CDC^) Delta, ppm 1.57 1. 87 4.09 7. 00 7.84 9. 40 -Empirical formula: C #_H 4,hexyl-3,4-(m) 4;hexyl-2,5-(m) 4 ; h e x y l - l , 6 - ( t ) 4;phenoxy-2,6-(d) 4;phenoxy-3,5-(d) 2;formyl (s) J,Hz 2 0H 2 2 ° 4 M.W. = 326 .40 Calc. Found C 7 3 . 6 0 73-69 H 6 .79 6 .74 0 1 9 . 6 1 Difference + 0. 09 - 0 . 05 8.3 8.3 Preparation of l-Hydroxy-6-para-formyIphenoxyhexane (MW 222) (Compound V) p-Hydroxybenzaldehyde ( 6 . 1 g , 0 . 0 5 mole) was dissolved in dry DMF (15 ml). Sodium hydride (1.2g, 10% excess) was added. The sodium hydride was allowed to react with the hydroxybenzaldehyde, (gentle heating), u n t i l the evo-l u t i o n of hydrogen was complete. 6-Chlorohexanol ( 6 . 8 3 g , 0 . 0 5 mole) was then added and the mixture s t i r r e d at room temperature for 24 hours. A c a t a l y t i c amount of potassium iodide was used. The reaction -62-was protected from moisture by the use of a calcium chloride drying tube. The whole reaction mixture was then poured into a 1 l i t r e separatory funnel and 350 ml methylene chloride added. The rest of the i s o l a t i o n procedure was si m i l a r to that a l -ready described for 1,6-bis-para-TormyIphenoxyhexane. On evaporating.off the solvent, a yellowish o i l was obtained. Yield 9.8g (88%). No attempt was made to purify the o i l further. NMR Data (CDC13, 60 MHz) Delta, ppm fl H J, Hz 1.48 8,hexyl -2 ,3 ,4 ,5-(m) 3-63 2;a-hydroxy (t) 3-97 2,a-phenoxy (t) 6.86 2;phenoxy-3,5-(d) 8.3 7.69 2,phenoxy-2,6-(d) 8.3 9.68 l;formyl (s) Mass Spectral Data M/e I M/e I 224 6 113 8 223 11 112 8 222 40 (parent) 111 17 (m/2e) 204 13 110 7 123 50 55 100 122 69 31 25 121 76 - 6 3 -Synthesis of 5 -[( 4-( 6-Hydroxy-l-hexoxy )phenyl] - 1 0 , 1 5 ,, 2 0 -t r l t o l y I p o r p h y r i n (HV,T 77 3) (Compound VI) l-Hydroxy-6-para-formylphenoxyhexane, ( 9 - 3 g , .0.04 mole) and 14.2g p-tolualdehyde (0.12 mole) were mixed with 500 ml of hot propionic acid. Pyrrole ( 1 0 . 9 g , 0 .16 mole) was added and the reaction mixture refluxed for one hour. After cooling the reaction mixture was f i l t e r e d and the purple c r y s t a l s washed with methanol. The i s o l a t i o n procedure followed was that already described for 5 - ( 4-hydroxyphenyl ) - 1 0 , 1 5 , 2 0-tritolylporphyrin. Tic showed the porphin to have an R f value of 0.11. On r e c r y s t a l l i s a t i o n from methylene chloride-ethanol, the por-phin came out as shiny purple needles. Yield 1 . 4 g ( 4 . 5 £ ) . Rn-R =-CH 3 ' R^ = - 0-(CH 2) 6-OH - 6 4 -NMR Data (CDCl,) D e l t a , ppm fl H 1.25 8 ;hexy l - 2 ,3 ,4 ,5-(ir:) 2.49 9 ; t o l y l (me thy l ) ( s ) 3.36 2 , a - h yd rox y ( t ) 3.71 2 ;a -phenoxy ( t ) . 6 .93 4 ; phenoxy - 2 , 3 , 5 , 6 -AB q u a r t e i 7. 32 - 6 ; t o l y l - 3 , 5 - ( d ) 8.01 6 ; t o l y l - 2 , 6 - ( d ) .8.85 8 ; 8 - p y r r o l e ( s ) r i c a 1 f o r m u l a : C 5 3 N 4 K 4 S ° 2 M. W . = 773-00 C a l c . Found D i f f e r e n c e C 82. 35 82.09 - 0 . 2 6 K 6. 26 6.31 +0.05 N 7. 25 7.51 +0.26 0 4.14 -Mass S p e c t r a l Data M/e I M/e I 834 26 (P+Cu) 605 62 775 8 556 16 774 23 555 63 773 42 ( p a r e n t ) 505 68 767 8 455 81 755 29 405 57 705 28 387 100 655 39 331 96 - 6 5 -Synthesis of 5 ,10,15-Tri-p-anisy1-20- [ 4 - [ 6 - [p-(10,15,20-tri- p-anlsyl -5-porphlnyl)-phenoxy]hexoxy]phenyl]porphine (M.W. = 1524) (Compound VII) • 0-002 mole) and p-anisaldehyde ( 5 - 0 g , 0.036 mole) were mixed with 100 ml of 1:1 propionic acid-ethylbenzene. Pyrrole ( 3 - 3 g , 0.05 mole) was added and the reaction mix-ture refluxed for one hour, and then taken to dryness under vacuum by means of a rotary evaporator. The r e s u l t i n g black tar was washed b r i e f l y with water, and then with d i l u t e ammonium hydroxide. The s l i g h t l y wet material was t r i t u r a t e d with a minimum amount of methanol on a steam bath u n t i l the purple crystals of the porphyrins were free from tar. The slurry was then stored overnight in a freezer. The purple s o l i d was f i l t e r e d o ff and washed with methanol and then dried. Yield of crude porphyrins was 1.5g-Tic of the porphyrins showed two spots, tetraanisylporphin ( R ~ 0.56) and the dimeric porphin (R f 0.3D. R 1 - R 6 = - 0 - C H 3 1 ,6-Bzs-para-formylphenoxyhexane (0.8g, -66-Th e m a t e r i a l was d i s s o l v e d i n a minimal amount of methylene c h l o r i d e and chromatographed on a 60 x 5 cm column of alumina u s i n g methylene c h l o r i d e as the e l u a n t . The f i r s t band e l u t e d from the column was the t e t r a a n i s y l p o r p h i n . The dimeric porphin took 6 hours to be e l u t e d from the column. This f r a c t i o n c o n t a i n i n g the dimer was r e c r y s t a l -l i s e d from methylene c h l o r i d e - e t h a n o l to g i v e 41 mg (1.1%) of the p o r p h y r i n . NMR Data (CDC1-) D e l t a , ppm # H J , Kz 1. 54 4;hexyl-3,4-(m) 2. 02 4;hexyl-2,5-(m) 4. 12 l8;methoxy (s) 4. 34 4 ; h e x y l - l , 6 - ( t ) 7. 34 l 6 ; a n i s y l - 2 , 6 - ( d ) 8. 17 l 6 ; a n i s y l - 3 , 5 - ( d ) 8. 90 16,6-pyrrole (s) - 6 7 -Mass Spectral Data M/e I M/e I_ 1528 3 635 10 1527 5 548 12 1526 6 484 10 1525 6 387 26 1524 (parent) 3 357 19 1522 3 342 10 920 4 268 11 852 3 851 4 798 13 786 46 785 100 77 6 35 764 11 763 9 762 (m/2e) 13 724 44 - 6 8 -Synthesis of 5,10,15-Tri-p-toIyl-20- [4- [ 6 - [p-(10,15,20-tri-p-toly1-5-porphinyl)- phenoxy]hexoxy]phenyl]porphine. (TTP-0-C^-O-TTP) (Compound V i l l a ) A mixture of l.OOg (1.49 mmoles) of 5-(4-hydroxypheny1)-10, 1 5 , 2 0 - t r i t o l y l p o r p h y r i n (TTP-OH), 3-0g crushed anhydrous potassium carbonate and 341 mg (0 . 8 mmole) 1,6-ditosyloX^— hexane was s t i r r e d magnetically with 25ml of DMF for 24 hours at room temperature. The reaction mixture was then f i l t e r e d to remove potassium carbonate. Water ( 10ml) was added to the f i l t r a t e . The water-DMF solvent was removed with the aid of a rotary evaporator to leave a purple p r e c i p i -tate. Tic of the pr e c i p i t a t e showed three spots. The most intense spot moving with the solvent front contained the dimer (TTP-0-Cg-O-TTP). Two less intense spots (R f values 0.11 and 0 . 3 1 ) were due to the hydroxylated porphins, TTF-0-C/--0H and TTP-OH respectively. -69-Th e p r e c i p i t a t e was d i s s o l v e d i n 200 ml methylene c h l o r i d e and chromatographed on a 25 x 2 cm alumina column using methylene c h l o r i d e as the eluant. The major band which moved with the solvent f r o n t contained the dimer. This band was c o l l e c t e d , and a f t e r r e c r y s t a l l i s a t i o n from methylene c h l o r i d e - e t h a n o l 807 mg (76%) of shiny purple c r y s t a l s were obtained. NMR Data (CDClO D e l t a , ppm ti H J , Hz -2.71 4,pyrrole N-H (s) 1.75 4;hexyl-3,4-(m) 2.02 4;hexyl-2,5-(m) 2.63-2.65 18 ;methyl (2s) 4.21 4 ; h e x y l - l , 6 - ( t ) 7.54 l 6 ; t o l y l - 2 , 6 - ( 2 d ) 3.1, 4.0 8.14 l 6 ; t o l y l - 3 , 5 - ( 2 d ) 3.1, 4.0 8.84 l 6 ; B - p y r r o l e ( s) i - 7 0 -Mass S p e c t r a l Data M/e I M/e I 1550 11 (P+2Cu) 554 22 1489 13 (P+Cu) 553 2 8 143C 9 552 32 1429 11 551 42 1428 10 (parent) 550 21 819 15 367 23 818 21 366 26 817 16 315. 25 816 10 314 22 815 17 306 36 775 33 305 40 744 91 290 39 734 89 149 67 733 90 91 100 726 94 714 88 (m/2e) 673 13 672 82 641 55 627 61 626 39 625 58 -71-A l t e r n a t i v e S y n t h e s i s of 5 , 1 0 , 1 5 - T r l - p - t o l y l - 2 0 - [4-[6- [ P -(10,15, 2 0 - t r i - p - t o l y l - 5 - p o r p h i n y 1 )phenoxy] hexoxy] phenyl]  porphine. (TTP-0-Cg-O-TTP) A mixture of l.Og (1.49 mmole) of 5 -(4-hydroxypheny1)-1 0 , 1 5 , 2 0 - t r i t c l y l p o r p h y r i n and 0.35g sodium hydride (14.5 mmole) was allowed to r e a c t u n t i l the e v o l u t i o n of hydro-gen was complete ( the mixture turned green). The r e a c t i o n was c a r r i e d out i n 25 ml of dry DJY1F. 1,6-Dibromohexane (181 mg, 0.74 mmole) was then added. The r e a c t i o n mixture was s t i r r e d f o r 48 hours at room temperature. The product was p r e c i p i t a t e d by pouring the r e a c t i o n mixture i n t o 100 ml of a 10A aqueous methanol s o l u t i o n , and then h e a t i n g the mixture to coagulate the p o r p h y r i n . The product was f i l t e r e d o f f , d r i e d at 100°C and then chromatographed on a 20 x 2 cm alumina column u s i n g methylene c h l o r i d e as the eluant. The major band which moved with the so l v e n t f r o n t contained the dimer. T h i s band was c o l l e c t e d and r e c r y s t a l l i s e d from methylene c h l o r i d e - e t h a n o l t o y i e l d 765 mg (12%) of the p o r p h y r i n dimer. Nmr and "mass s p e c t r a l data were i d e n t i c a l t o that a l r e a d y r e p o r t e d . E m p i r i c a l formula: Cioo N 8^2 H82 M.W. = 1427 .82 C a l c . Found D i f f e r e n c e c 84.12 84.10 -0.02 H 5 .78 5.56 -0. 22 N 7.85 8.20 + 0. 35 0 2 . 2 5 _ — -72-Absorption C h a r a c t e r i s t i c s of TTP-0-C^-O-TTP - 3 Amax, nm (EX 10 ) 419(712) 487(7.0)sh 518(34.2) 552(16.5) 593(10.6) 649(9.5) sh=shoulder Synthesis of 5 ,10 ,15-Triphenyl-20- [4-[6-(10,15,20-tripheny1-5-porphinyl)phenoxy]hexoxy]phenyl]porphlne (TPP-0-C^-O-TPP) (Compound V H I b ) A mixture of 5-(4-hydroxyphenyl)-10,15,20-triphenyl-porphyrin ( l . l g , 1.74 mmoles), 400 mg ( 0 . 9 3 mmoles) 1,6-oxy ditosylhexane were s t i r r e d f o r 48 hours i n the presence of 1.2g crushed anhydrous potassium carbonate i n 20 ml of dry DMF. The r e s t of the i s o l a t i o n procedure was s i m i l a r to that already described f o r TTP-0-Cg-O-TTP. On r e c r y s t a l l i s a t i o n from methylene c h l o r i d e - e t h a n o l , the dlmerlc tetraphenyIporphyrin came out as a pu r p l e , m i c r o - c r y s t a l l i n e s o l i d . Y i e l d 903 mg (77%). - 7 3 -Empirical formula: C Q l^NgOpH^ 0 K. W. = 1343 .66 • Calc . Found Difference C 84. 03 8 3 - 9 1 -0.12 H 5 . 2 5 5-27 + 0. 02 N 8.34 8. 22 -0. 12 0 2. 38 - -NKR Data (CDC13) Delta, ppm fl H •2.74 4;pyrrole N-K (s) 1 .80 4;hexyl-3,4-(m) 1.98 4;hexyl-2,5-(m) 4 . 2 8 4 ; h e x y l - l , 6 - ( t ) 7 . 7 3 l6,phenyl -2 ,6-(m) 8.15 l6,phenyl -3 ,5-(m) 8 . 8 6 l 6 ; B - p y r r o l e (m) -74-Mass Spectral Data M/e I M/e I 1466 16 (P+2Cu) 618 29 1405 15 (P+Cu) ' 616 31 1404 14 615 37 1403 15 614 13 1402 13 613 15 1347 15 589 30 1346 14 543 32 1345 15 511 24 1344 14 (parent) 433 18 1272 12 432 17 1271 13 355 19 1270 12 342 26 1269 13 341 28 838 14 316 64 837 13 293 33 836 14 256 37 835 14 149 83 779 8 108 80 733 9 107 100 717 16 716 16 703 17 693 22 672 15 (m/2e) 671 18 642 23 630 53 -75-PART (B) - TETRAPHENYLBACTERIOCHLORINS AND CHLORINS (MONOMERS AND DIMERS) Synthesis of meso-Tetraphenylbacteriochlorln (Compound IXa) A mixture of l g ( 1 . 6 mmoles) of meso-tetrapheny1-porphyrin, 0 . 6 g of p-toluenesulfonyIhydrazine, 2 . 0 g of anhydrous potassium carbonate, and 75 ml of dry pyridine was heated with s t i r r i n g at 105°C, under nitrogen and in the dark. Heating and s t i r r i n g was continued for 12 hours, 0 . 3 g of p-toluenesulfonylhydrazine being added every hour. Analysis of a sample of the reaction mixture showed the absence of any tetraphenylchlorin (no 652 nm band, in the v i s i b l e spectrum). There was a strong band at 7^2 nm due to the bacteriochlorin. The reaction mixture was allowed t o stand under n i -trogen at room temperature for an extra 8 hours. The whole reaction mixture was then added to a mixture of 500 ml of - 7 6 -benzene and 3 0 0 ml of 10% aqueous sodium hydroxide and the mixture was digested for 2 hours on a steam bath. After cooling, the benzene layer was washed 'thrice with a t o t a l of 5 0 0 ml of cold 3N hydrochloric acid, aqueous sodium bicarbonate solution and then with water. The benzene extract was then dried over anhydrous sodium sulphate for two hours (in the dark). After f i l t r a t i o n to remove •the sodium sulphate, the benzene extract was then evapor-ated. The residue was r e c r y s t a l l i s e d from deoxygenated toluene to afford 0 . 4 7 g (47%) of reddish-purple bacteric-chl o r i n c r y s t a l s . ' Absorption Characteristics of TPBC (Monomer) Xmax, nm 356 3 7 8 4 l 8 522 7 4 c Ratios 2 . 6 3 - 3 1 . 0 1 . 4 2 . 7 Cone. 4.6 x 10 M o L i t . ^ 2 (Benzene) Xmax, nm 356 3 7 8 5 2 0 742 e x 1 0 ~ 3 1 3 0 1 6 0 6 0 1 2 0 NMR Data (CDCl^) Delta, ppm fl H J , Hz - 1 . 3 0 2;pyrrole N-H (s) 3 . 9 2 8;-CH2CH2-(s) 7.52 20;ArH (m) 7.85 4 ; 6 - p y r r o l e (d) 2 . 0 -77-meso-Tetraphenylbacteriochlorin, 400 mg (0.65 mmoles), and 147 mg (0.65 mmoles) 2,3-dichloro-5,6-dicyanobenzo-quinone (DDQ) were s t i r r e d together in 300 ml of benzene at room temperature for one hour. The benzene solution was then washed with 5% aqueous sodium bisulphite solution, 5% aqueous sodium hydroxide solution, saturated aqueous sodium bicarbonate solution, water, and was dried over I anhydrous sodium sulphate. Removal of solvent gave 350 mg of a residue that was r e c r y s t a l l i s e d from 30 ml of deoxygen-ated benzene to afford 310 mg (78% y i e l d ) of tetraphenyl-ch l o r l n . -78-Absorption Characteristics of TPC (Won OIK er) Amax, nm 418 518 542 596 651 Ratios 30 2.2 1.'6 1.0 4.6 C o n e . 4.9 x 10 Mo L i t . ^ (Benzene) Amax, nm 419 517 5 4 l 598 652 e x 1 0 " 3 190 16 12 6.1 42 NMR Data (CDCl^) Delta, ppm U H -1.30 2,pyrrole N-K (s) 4.10 4;-CK 2CK 2-(s) 7 .6-8 .5 26;ArH, 6-pyrrole (m) The band (6=7.6 - 8.5 p.p.m.) could be resolved into a s i n g l e t , area 2H at 6 8.34 p.p.m. and AB quartet of area 4K ( 6 a 8.10,6g 8.49, J A B = / 4 - 5 Hz) assigned to the chlorin ring protons. Alternative Synthesis of mgso-Tetraphenylchlorin meso-Tetrapbenylbacteriochlorin 400 mg, (0 .65 mmole) was chromatographed on a 60 x 5.cm column of alumina using dichloromethane as the eluant. The bacteriochlorin moved down the column slowly and was being oxidized to the chlo r i n (green colouration on the column). The chlori n was then eluted from the column using 20:1 methylene chloride-methanol. A v i s i b l e spectrum of the eluate Indicated that a l l the bacteriochlorin had been oxidized to the c h l o r i n (no 742 nm band). The solvent was then removed and the residue r e c r y s t a l l i s e d from 25 ml of - 7 9 -deoxygenated benzene to afford 290 mg (73% y i e l d ) t e t r a -phenylchlorln. The absorption spectrum in methylene chloride was i d e n t i c a l to that already reported. Synthesis of 5- [4-(6-Hydroxy-l-hexoxy)pheny1]-10,15,20-t r i t o l y l b a c t e r i o c h l o r i n (M.W. 777) (Compound Xa) R 3 R 1 - R 3 = - C H 3 , R 1 ] = - 0 - ( C H 2 ) 6 - O H 5_ [H_ (6-Hydroxy-l-hexoxy )phenyl] - 1 0 , 1 5 , 2 0 - t r i t o l y l -porphyrin (500mg, 0.65 mmole) was reduced to the correspond-ing b a c t e r i o c h l o r i n using p-toluenesulfonyhydrazine in a procedure s i m i l a r to that already described for the pre-paration of meso-tetraphenylbacteriochlorin. This b a c t e r i o c h l o r i n was r e c r y s t a l l i s e d from de-oxygenated toluene to y i e l d 376 mg (75% y i e l d ) of reddish-purple shiny c r y s t a l s . - 8 0 -NMR Data (CDCIO Delta H H - 1 . 31 2;pyrrole N-K (s) 1. 53 8;hexyl-2,3,4 35-(m) 2. 68 9 j t o l y l (methyl) (2s 3-72 2;a-hydroxy-(t) 4. 14 2, a-phenoxyr-(t) 4. 30 8;-CH 2-CH 2-(s) 7. 51 8jtolyl-3,5-(m) 8. 10 8;tolyl-2,6-(m) 8. 55 4;B-pyrrole (s) Mass S p e c t r a l Data M/e I M/e I 843 9 655 12 842 10 605 13 841 10 555 10 840 14 505 13 839 13 455 17 838 15 (P+Cu) 405 16 837 21 391 11 836 6 386 9 777 5 (parent) 385 10 774 63 381 19 773 100 343 25 772 12 331 27 755 16 754 17 • 743 13 672 20 - 8 l -Synthesls of 5- [ 4 - ( 6-Hydroxy-l-hexoxy)phenyl] - 1 0 , 1 5 , 2 0 -t r i t o i y l c h l o r i n (M.W. 775) (Compound Xb) R 5 R1-R3=-CH3, R 4 = - 0 -(CH 2)g - 0H 5_ [ 4 - ( 6-Hydroxy-l-hexoxy)phenyl] - 1 0 , 1 5 , 2 0-tritolyl-bac t e r i o c h l o r i n (300 mg, 0 . 3 8 mmole) was oxidized to the chlo r i n using 86 mg (0 . 3 8 mmole) of DDQ following a pro-cedure similar to that already described for the preparation of meso-tetraphenylchlorin. This c h l o r i n was r e c r y s t a l -l i s e d from deoxygenated toluene to afford 193 mg (64% y i e l d ) of shiny purplish c r y s t a l s . When dissolved in methylene chloride t h i s c h l o r i n was green. Tic on s i l i c a gel plates using methylene chloride as eluant showed two-spots (R f values 0 . 1 2 and 0 . 1 5 ) corresponding to the two Isomers possible for thi s c h l o r i n . It was not possible to separate the two isomers on a chromatographic column (alumina or s i l i c a g e l ) , due to the oxidation of the chlorins on chromatographic columns. - 8 2 -NMR Data CDCl^) D e l t a , ppm -1.32,-1.41 1. 56 2. 59 3.68 3-95 4.12 7.45-7.64 7.98-8.18 8.43-8.56 # H 2,pyrrole N-H (2s) 8;hexyl-2,3,4,5-(m) 9; t o l y l ( m e t h y l ) (3s) 2,cx-hydroxy-(t) 2;a-phenoxy-(t) 4;-CH 2CH 2-(s) 8,tolyl-3,5-(m) 8;tolyl-2,6-(m) 6,B-pyrrole (3s) Dimeric b a c t e r i o c h l o r i n s , and c h l o r i n s were a l l synthesized i n the same manner as the monomeric b a c t e r i o -c h l o r i n s and c h l o r i n s . The reducing agent was p-toluene-s u l f o n y l h y d r a z i n e and the o x i d i z i n g agent was 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ). Synthesis of 5,10,15-Trl-p-tolyl-20-[4-[6- [p-(10,15,20-tri-p-toly1-5 - b a c t e r l o c h l o r i n y l ) p h e n o x y ] h e x o x y ] p h e n y l ] b a c t e r i o c h l o r i n (M.W. 1436) (Compound XIa) o V W -83-• Recrys t a l l i s e d from deoxygenated toluene-hexane, and dried in vacuo at 120°C for 12 hours. Yield 246 mg (65%). NMR Data (CDCl^ Delta, ppm fl H -1 .32 4;pyrrole N-H (s) 1.73-2.02 6,hexyl-2,3 ,4,5-(m) 2 . 5 7,2 . 6 3 l 8,tolyl(methyl) (2s) 3-27 4 , - 0-CH 2-(bt) 4 . 0 8 - 4 . 1 6 l6,bact.-CH 2-CH 2-(bs) 7 . 4 3 l 6 ; t o l y l - 3 , 5 - ( m ) 7 . 6 8 - 7 - 9 4 l 6;tolyl-2 , 6-(m) 8 . 4 4 - 8 . 5 8 8 , 3-pyrrole (bs) Empirical formula: ^100^90^8^ M.W. = 1435. 88 Calc. Found Difference C 83.65 83.85 +0. 20 H 6. 32 6.19 -0 . 13 N 7. 80 7.86 + 0. 06 0 2. 23 _ — -84-Synthesis of 5,10,15-Tri-p-toIyl-20-[4-[6-[p-(10,15,20-tri-p- tolyl-5-chlorinyl)phenoxy]hexoxy]phenyl]chlorin ( M . W . 1432) (Compound Xlb) R.-R,=-CH 5 , 1 0 , 1 5-Tri-p-tolyl - 2 0 - [4- [6-[p-( 1 0 , 1 5 , 2 0-tri-p-tolyl-5-bacterlochloriny 1)phenoxy]hexoxy]phenyl]bacteriochlorin, 200 mg (0.14 mmole) was oxidized using 31 mg (0.14 mmole) of DDQ following the standard procedure. The y i e l d of the c h l o r i n dimer afte r r e c r y s t a l l i s a t i o n from deoxygenated toluene-hexane was 121 mg (60%). -----When dissolved in methylene chloride t h i s c h l o r i n was greenish. Tic on s i l i c a gel plates with methylene chloride as the eluant showed three spots of approximately equal intensity (R^ . values 0 . 4 5 , 0.55 and 0.75) corresponding to the three possible isomers. The isomers were not sep-arable on any chromatographic column (alumina or s i l i c a g e l ) . The absorption spectrum of t h i s mixture of chlorins showed the complete absence of any bacteriochlorin. As expected, the proton magnetic resonance spectrum was complex. - 8 5 -W:T. Date (CDCl^) D e l t a , ppm fl H -1.41,-1 .76 4;pyrrole N-H ( 2 s ) 2 . 0 3 , 2 . 3 7 8,hexyl - 2 , 3 , 4 , 5-(bm) 2 . 6 0 1 8 ;methyl ( 3 s ) 4 .13 8 ; c h l o r i n - C H 2 - C H 2 - ( 2 s ) 4.40 4;-CH 2 - 0-(bt) 7 .46-7.70 l 6 ; t o l y l - 3 , 5 - ( b m ) 7 . 9 7 - 8 . 5 4 l 6 , t o l y l - 2 , 6 - ( b m ) 8 . 6 5 - 8 . 8 6 1 2 ; 6 - p y r r o l e (bs) E m p i r i c a l formula: C i o o H 8 6 K 8 ° 2 M.W. = 1 4 3 1 . 8 5 C a l c . Found D i f f e r e n c e c 8 3 . 8 9 8 3 . 7 0 -0 . 19 H 6 . 0 5 5 . 9 8 - 0 . 0 7 N 7 . 8 3 7 . 9 9 +0.16 0 2 . 2 3 -86-PART (C) - ZINC METALLO-DERIVATIVES OF THE MffSP-TETRA-PHENYLPORPHYRINS, CHLORINS AND BACTERIOCHLORINS (MONOMERS AND DIMERS) Synthesis of Zinc meso-Tetraphenylporphin (ZnTPP) (Compound Xlla) A mixture of 0 . 6 g (0.9& mmole) of TPP, and 0 . 6 g (2.7 mmoie) zinc acetate dihydrate was boiled gently i n 75ml of dry pyridine. After conversion to the zinc metalloporphine was complete (approximately 15 minutes), as indicated by the absence of free base absorption bands in the v i s i b l e spectrum, the solution was transferred to a separatory funnel with 80ml of benzene. Water was added to the separatory funnel, and the r e s u l t i n g benzene layer was washed several times with water to completely remove the pyridine and inorganic s a l t s . A f i n a l wash with IM ammonium chloride was necessary to break the emulsions. The benzene layer was dried over anhydrous sodium sulphate. The r e s u l t i n g benzene solution was - 8 7 -evaporated to dryness under vacuum to y i e l d the s o l i d metalloporphine. R e c r y s t a l l i s a t i o n of the of the s o l i d was accomplished by slowly adding methanol to a concentrated methylene chloride solution of the metalloporphine. Purple, shiny crystals of ZnTPP were obtained. Yield 490 mg ( 74% ) . Absorption Characteristics of ZnTPP (Monomer) Amax, nm 418 548 587 R £ t i o s ^ 6 5.5 1.0 cone. 2.8 x 1 0 ~ 5 ^ L i t . (Benzene) Amax, nm 419 550 587 e x 1 0 " 3 590 23 3-5 Empirical formula: C^^N^H^gZn M.W. = 6 7 8 . 1 1 Calc. Found Difference c 77.94 77 . 8 0 - 0 . 1 4 H 4. 16 4. 39 +0.23 N 8 . 2 6 8 . 3 9 +0.13 Zn 9. 64 _ — - 8 8 -Synthesis of Zinc Tetraphenylporphin Dimer (M.W. 1470.4) (Compound Xllb) The compound was synthesized as described above for zinc meso-tetraphenylporphin. 15 mg ( 0 . 0 1 mmole) of the free base porphyrin dimer (Compound VHIb) was used i n i t i a l l y . Purple, shiny c r y s t a l s of the zinc porphine cimer were obtained. Yield 10 mg (6l%). Absorption Characteristics of ZnTPP (Dimer) Xmax, nm 419 547 586 Ratios 141 5-2 1 .0 -5 Cone. 3.6 xlO M. - 8 9 -Mass Spectral Data "M/e I M/e I 1476 9 1352 17 1475 11 1060 36 1474 12 793 18 1473 14 735 4 1472 14 694 81 1471 9 (parent) 488 76 l 4 n 15 310 96 1410 8 221 100 Synthesis of Zinc meso-TetraphenyIchlorin (ZnTPC) (Compound X H I a ) 1 1 9 A mixture of meso-tetraphenyIchlorin (TPC), 240 mg (0.39 mmole), and 240 mg (1.1 mmole) zinc acetate dihydrate was boiled gently, with s t i r r i n g under nitrogen, i n com-plete darkness, in 35 ml of dry pyridine. After conversion - 9 0 -to the zinc metallochlorin was complete (approximately 25 minutes), as indicated by the abse'nce of free base absorption bands in the v i s i b l e spectrum, the solution was transferred to a separatory funnel with about 40 ml of deoxygenated benzene. (Solvent deoxygenation was effected by bubbling nitrogen through the solvent for at least 30 minutes). Water was added to the separatory funnel, and the r e s u l t i n g benzene layer was washed several times with water to completely remove the pyridine and inorganic s a l t s . A f i n a l wash with IM ammonium chloride was neces-sary to break emulsions. The benzene layer was dried over anhydrous sodium sulphate. The r e s u l t i n g benzene solution was evaporated to dryness under vacuum to y i e l d the s o l i d metallochlorin. The s o l i d was r e c r y s t a l l i s e d from deoxygenated benzene. The y i e l d of the ZnTPC was 226 mg (85%) . Absorption Characteristics of ZnTPC (Monomer) 521 569 593 628 1.0 1.1 1 .8 9-3 Cone. 2.9 x 10~5 M. 522 568 590 630 6.1 6 . 9 10 .5 57.0 Amax, nm 424 Ratios 540 119 L i t . 7 (Benzene. Amax, nm 422 e x 10~ 3 326 -91-Empirical formula: C^N^H^Zn M.W. = 6 8 0 . 1 3 Calc . Found Difference C 77-70 77.46 -0.24 H 4.45 4.60 + 0.15 N 8.24 8. 29 + 0.05 Zn 9. 61 Synthesis of Zinc Tetraphenylchlorin Dimer (K.W. 1474.4) (Compound XHIb) The free base c h l o r i n dimer, 5 > 1 0 , 1 5-triphenyl - 2 0 -[4-[6-(10,15,20-triphenyl -5-chloriny1)phenoxy]hexoxy]phenyl] c h l o r i n , was prepared as described for i t s t o l y l analogue (Compound Xlb). The zinc (II) complex was prepared using 119 the standard procedure . The y i e l d was 23 mg ( 7 2 % ) (based on the free base c h l o r i n dimer). No attempt was made to separate the three (zinc tetraphenylchlorin dimer) isomers. Tic on s i l i c a gel plates, using methylene chloride as the eluant, showed 3 green spots (R f values 0 . 5 9 , -92-0.71 and 0 . 8 l ) . Absorption C h a r a c t e r i s t i c s of Zinc TPC (Dimer) Amax, nm 423 522 569 595 - 628 Ratios 51 .9 L O 1.2 2 . 0 9-5 -5 5.6 x 10 M. Mass S p e c t r a l Data M/e I M/e I 1476 10 1061 36 1475 11 1060 32 1474 13 (parent) 793 44 1473 14 792 36 1472 13 . 737 6 1471 10 694 78 1353 18 488 76 1352 17 310 98 1351 8 221 100 Synthesis of Zinc meso-Tetraphenylbacteriochlorin (ZnTPBC) (Compound XlVa) V R 4 = H -93-A mixture of meso-tetraphenylbacteriochlorin (TPBC),° 60 mg ( 0 . 0 9 7 mmole), and 60 mg ( 0 . 2 8 mmole) zinc acetate dihydrate, was boiled gently, with s t i r r i n g under nitrogen in complete darkness in 20 ml of dry pyridine. The comple conversion to the zinc metallobacteriochlorin took about 30 minutes. The work-up procedure was e s s e n t i a l l y the same as that described for ZnTPC. The crude ZnTPBC mixture showed two spots on t i c , using benzene as eluant. The more intense spot moving with the solvent front was that due to ZnTPBC. The less intense green spot (R^ , value 0 . 8 7 ) was due to ZnTPC. The ZnTPBC mixture was quickly chromatographed on a 10 x 5 cm alumina chromatographic column using benzene as eluant. The major band which moved with the solvent front was collected and evaporated. The zinc metallo-bacteriochlorin s o l i d was r e c r y s t a l l i s e d from deoxygen-ated benzene to y i e l d 56 mg (85%) of shiny purplish-red c r y s t a l s . Absorption Characteristics of Zinc TPBC (Monomer) Xmax, nm 357 378 523 7 4 l Ratios 2 . 2 5-1 1-0 2 . 1 Cone. 1.5 x 10 jf # NMR Data. ( C D C 1 3 ) Delta, ppm fl H J, Hz 4.12 8;-CH 2CH 2-(s) 7.54 12;phenyl-3,4,5-(m) 7.86 8;phenyl-2,6-(m) 8.49 4;B-pyrrole (d) 2 . 0 -94-Synthesis of Zinc T e t r a p h e n y l b a c t e r l o c h l o r l n Dimer (M.W. 1478.4) (Compound XlVb). The free base b a c t e r i o c h l o r i n dimer, 5,10,15-tri-phenyl-20-[4-[6-(10,15,20-tripheny1-5-bacteriochloriny1)-phenoxy]hexoxy]phenyl]bacteriochlorin was prepared as described f o r i t s t o l y l analogue (Compound XIa). The zinc (II) complex was prepared f o l l o w i n g the procedure described f o r the p r e p a r a t i o n of ZnTPBC. The y i e l d was 47 mg (70%) (based on the fr e e base b a c t e r i o c h l o r i n dimer). Absorption C h a r a c t e r i s t i c s of Zinc TPBC (Dimer) Xmax, nm 356 378 522 741 Rat i o s 2.3 5-2 1.0 2.0 -4 Conee 1.3 x 10 M« - 9 5 -Mass Spectral Data M/e I M/e I 1478 5 (parent) 1060 42 1477 7 793 32 1476 9 739 36 (m/2e) 1475 13 694 76 1474 17 489 79 1354 10 488 68 1061 41 310 100 -96-P A R T ( D ) - A T T E M P T E D S Y N T H E S I S O F TETRA-MESO-[p, p ' - ( 3 , 3 ' - P H E N O X Y P R O P O X Y P H E N Y L ) > 5 ™ T J-BJ5PORPHYRIN M o l e c u l a r f o r m u l a = C^ QQH^gNgOg (Compound X X ) 53 I n a r e c e n t paper , Kagan et a l . r e p o r t e d t h e s y n -t h e s i s o f a n o v e l e t r a t i - f c i s p o r p h y r i n . We se t out t o s y n t h e s i z e a v e r y s i m i l a r s t r a t i - M s p o r p h y r i n . (Compound XX) S y n t h e s i s o f p -3 -B romopropoxybenza ldehyde (Compound X V ) A m i x t u r e o f p - h y d r o x y b e n z a l d e h y d e , 27.7g ( 0 .23 m o l e s ) , 5«0g o f anhydrous p o t a s s i u m c a r b o n a t e and 68.8g (0.34 mo le s ) o f 1 , 3 -d ib romopropane was s t i r r e d i n a m i n i -- 9 7 -mum volume (about 20 ml) of rea g e n t grade a c e t o n e , at room temperature f o r 48 h o u r s . The r e a c t i o n m i x t u r e was poured i n t o a 1 l i t r e s e p a r a t o r y f u n n e l and 400 ml of methylene c h l o r i d e added. The m i x t u r e was e x t r a c t e d t w i c e w i t h a t o t a l of 500 ml of 5% aqueous sodium h y d r o x i d e t o remove u n r e a c t e d hydroxybenzaldehyde.. The methylene c h l o r i d e e x t r a c t was washed t w i c e w i t h water and d r i e d over anhydrous sodium s u l p h a t e . The s o l v e n t s were r e -moved u s i n g a vacuum pump at 6 5 ° C , t o l e a v e behind a y e l l o w i s h o i l . 1 , 3-Dibromopropane i s f a i r l y v o l a t i l e and was thus removed w i t h the a i d of a vacuum pump. The y e l l o w i s h o i l was then d r i e d at 60° in vacuo. The y i e l d was 2 8 . l g (51%) of p - 3-bromopropoxybenzaldehyde. NK.r. Data (CDC1_) D e l t a , ppm # H J , Hz 2 . 3 5 2 ; p r o p y l - 2 ( t t ) 3 . 6 2 2;-CH 2-Br ( t ) 4 . 2 1 2;-CH 2-0-(t) 7 . 0 3 2;phenoxy - 2 , 6-(d) 8 . 6 7 . 8 5 2;phenoxy - 3 , 5-(d) 8 . 6 9 . 8 9 l ; f o r m y l ( s ) - 9 8 -Mass Spectral Data M/e I M/e I 246 3 122 21 245 9 121 38 244 16 120 6 243 7 (parent) 105 7 242 18 94 6 241 5 93 10 165 2 41 18 164 3 28 13 163 6 32 29 162 10 28 100 161 5 123 12 Synthesis of 5,10,15,20-Tetra-[p-(3-bromopropoxy)phenyl]porphyrin (M.W. 1162.7) (Compound XVI) Ri_R1, = _0-CH 2CH 2CH 2-Br -99-p-3-Bromopropoxybenzaldehyde (l8.5g, 0.076 mole) and 5.2g (0.077 mole) of p y r r o l e were added to 270 ml of propionic a c i d that was near b o i l i n g temperature. The r e a c t i o n was r e f l u x e d f o r one hour and -then taken to dry-ness under vacuum by means of a r o t a r y evaporator. The r e s u l t i n g black t a r was washed b r i e f l y with water, and then with d i l u t e ammonium hydroxide. The s l i g h t l y wet m a t e r i a l was t r i t u r a t e d with a minimum amount of methanol on a steam bath u n t i l the purple c r y s t a l s of the porphyrin were free from: t a r . The s l u r r y was then stored overnight, i n a f r e e z e r at -5°C. The purple s o l i d was f i l t e r e d o f f and washed with a minimal amount of methanol and then d r i e d . The m a t e r i a l was d i s s o l v e d i n 300 ml of methylene c h l o r i d e and chromatographed on a 60 x 5 cm column of alumina using methylene c h l o r i d e as the eluant. The por-p h y r i n band moved with the solvent f r o n t while a brown Impurity stuck on top of the column. The porphyrin was r e c r y s t a l l i s e d from methylene chloride-methanol to y i e l d 1.4g (6.3%) of shiny purple n e e d l e - l i k e c r y s t a l s . -10.0-NMR Data (CDC1-) D e l t a , pprr, a K J j Hz -2. 50 2 ; p y r r o l e N-H (s) 2. 74 8,propy 1 - 2 - ( t t ) 4. 01 8;-CH 2-Br ( t ) 4. 61 8;-CH 2-0- ( t ) 7. 50 8;phenoxy - 2 , 6 - (d) 2.9 8. 35 • 8;phenoxy - 3 , 5 - (d) 2.9 9. 10 8 ; 6 - p y r r o l e ( s ) Mass Spe c t r a l Data M/e I M/e I 1224 4 169 27 1223 5(P+Cu) 168 35 1222 6 167 31 1221 5 149 79 1162 15 ( p a r e n t ) 141 • 27 1161 18 121 33 1080 22 107 65 1067 38 94 76 1065 36 91 63 854 9 80 99 800 13 49 87 743 15 44 100 581 29 213 31 212 34 173 24 172 41 - 1 0 1 -A method was worked out for synthesizing 5 , 1 0 , 1 5 , 20-tetra- [p- ( 3-bromopropoxy )phenyl] porphyrin s t a r t i n g from 5 , 1 0 , 1 5 , 2 0-tetra - ( 4-hydroxyphenyl)porphyrin. The procedure i s as described below. Synthesis of 5 , 1 0 , 1 5 , 2 0-Tetra-(4-propionyIphenyl)porphyrin (M.W. = 9 0 3-D (Compound XVII) *4 R 1-R^=-0 2C-CH 2CH^ para-Hydroxybenzaldehyde (17.lg, 0.14 mole) was added to a mixture of 100 ml of propionic anhydride and 350 ml of propionic acid; and the mixture was refluxed. Pyrrole (9.4g, 0.14 mole) was then added. The reaction mixture was refluxed for one hour and then stood over-night at -5°C. The crude porphyrin (purple needles) was f i l t e r e d o f f and repeatedly washed with cold ethanol. The y i e l d was 6.7g (21.2%). - 1 0 2 -NMR Data (CDCl^ Delta, pprc ff H J, Hz 1.41 12;6-propionyl (t) 7 . 1 2 .79 8;a-propionyl (q) 7 .1 7 .51 8;phenoxy-2,6-(d) 8 . 2 8.22 8;phenoxy-3,5-(d) 8 . 2 8 . 8 8 8;B-pyrrole (s) Mass Spectral Data M/e I M/e I 906 6 649 11 905 10 575 12 904 14 465 2 903 18 (parent) 464 3 902 25 463 2 889 2 462 3 849 10 452 11 791 29 169 19 733 29 149 55 681 11 74 100 -103-Synthesis of 5 ,10,15,20-Tetra-(4-hydroxyphenyl)porphyrin (M.W. 6 7 8 . 8 ) (Compound XVIII) R1-R1|=-OH 5,10,15,20-Tetra-(4-prppionyIpheny1)porphyrin (6.5g, 7.1 mmoles) was refluxed for 20 hours in 95% ethanol containing 4 g of potassium hydroxide. The r e s u l t i n g green solution was f i l t e r e d , a c i d i f i e d with acetic acid, and then taken to dryness, y i e l d i n g an amorphous purple s o l i d which was very soluble i n ethanol and aqueous alk a l i n e solution. The s o l i d was taken up i n methylene chloride, f i l t e r e d and evaporated to dryness. It was r e c r y s t a l l i s e d from ethanol-water with a y i e l d of 3«47g (71 Empirical formula: Ci^Ni^oo 0^ M. W. = 678.75 Calc. Found Difference C 77.86 78.01 +0.15 H 4.46 4.41 -0.05 N 8.25 8.09 -0.16 0 9.43 mmm _ -104-Syntbesis of 5 ,10,1 5 ,20-Tetra- [p-(3-bromopropoxy)phenyl]porphyrin (Compound XVI) 5,10,15,20-Tetra-(4-hydroxyphenyl)porphyrin (3-0g, 4.4 mmoles) was s t i r r e d i n 35 ml of DMF with 1.8g of crushed sodium hydroxide. 1,3-Dibromopropane (17.8g, 88 mmoles) was then added q u i c k l y and the r e a c t i o n mixture s t i r r e d f o r 36 hours at room temperature. Ethanol (50 ml) was added to the green s o l u t i o n followed by 600 ml of water. The purple product was f i l t e r e d o f f and washed with absolute ethanol and then d r i e d . I t was chromatographed. on alumina with methylene c h l o r i d e as the eluant. The porphyrin moved with the solvent f r o n t and separated e a s i l y from any unreacted s t a r t i n g m a t e r i a l and from two slowly moving green and brown bands near the top of the column. A f t e r r e c r y s t a l l i s a t i o n from methylene c h l o r i d e -ethanol a very small crop of shiny purple c r y s t a l s was obtained. Y i e l d 87.4 mg (1.7%). The nmr spectrum was i d e n t i c a l to that already reported. -105-Synthesls of 5 , 10,15 ,20-Tetra-[(p'-formyI -3-phenoxy-p-propoxy)-phenyl]porphyrin.(M.W. = 1 3 2 7 . 6 ) (Compound XIX) * 4 R1-Ri j = -0-CH 2CH 2CH 2Olh-CH0 5 Ph=Phenyl A mixture of 1 .4g ( 1 . 2 mmoles) of 5 , 1 0 , 1 5 , 2 0 - t e t r a -[p-(3-bromopropoxy)phenyl]porphyrin, 1 .2g anhydrous po-tassium carbonate, 2.19g (24 mmoles) of p-hydroxybenzaldehyde were s t i r r e d for 48 hours in 15 ml of DMF at room temper-ature. The product was precipitated by pouring the re-action mixture into 100 ml of a 10% aqueous sodium hydroxide, and then heating the mixture to coagulate the porphyrin. The product was f i l t e r e d o ff and washed thoroughly with water, then b r i e f l y with methanol. The porphyrin was r e c r y s t a l l i s e d from methylene chloride-ethanol. Purple, shiny c r y s t a l s of the porphyrin were obtained. The y i e l d was 1.21g (76%). -106-NMR Data (CDC1-/TFA) D e l t a , ppm H H J , Hz 2. 60 8,propyl-2-(tt) 3-54 l6;propyl-l, 3-(m) 7. 23 8;B-phenoxy-3,5-(d) 8.6 7. 62 8;a-phenoxy-3,5-(d) 7.9 8.04 8;6-phenoxy-2,6-(d) 8.6 8. 50 8;a-phenoxy-2,6-(d) 7.9 8.62 8;B-pyrrole (s) 9.76 4-formyl (s) The mass spectrum showed the molecular ion at m/e = 1328, and the doubly charged ion m/2e = 664 as expected. Attempted Synthesis of Tetra-weso-[p,p'-(3,3'-phenoxy-pr op oxy phenyl) ] -s tret t-2? i s porphyrin. (Compound XX) 5,10,15,20-Tetra- [(p 1-formy1-3-phenoxy-p-propoxy)-phenyl]porphyrin 0.6g (0.45 mmoles) was r e f l u x e d i n 1130 ml (0.4 mM concentration) of p r o p i o n i c a c i d - e t h y l -benzene (1:1). P y r r o l e 0.12g (4 e q u i v a l e n t s ) was added, and the mixture r e f l u x e d f o r 1.5 hours. The solvent was removed under vacuum by means of a r o t a r y evaporator. The methylene c h l o r i d e - s o l u b l e products were c o l l e c t e d . They could not be eluted o f f any chromatographic column (alumina or s i l i c a g el) using methylene c h l o r i d e as the eluant. The e t r a t t - f c i s p o r p h y r i n could not be character-i z e d . -107-We believe that attempts to synthesize the s t r a t i -tisporphyrin (with a 3-carbon linkage) were unsuccessful because of the s t e r i c s t r a i n a r i s i n g from such a system. 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The absorption spectra of solutions of t e t r a a r y l b a c t e r i o -chlorin (monomers and dimers) were measured in 10mm quartz c e l l s . The structures of the compounds are as shown below each absorption spectrum. Unless otherwise s p e c i f i e d , the groups R^-R^ = H (for the monomers) and the groups R,-Rf = H (for the dimers). -118-- 1 1 9 -R 1-R 3 = -CH 3, R ;,=-0-(CH 2) 6-OH S o l v e n t 1 = Dichlorometbane/TFA S o l v e n t 2 = DMF S o l v e n t 3 = Di c h l o r o m e t h a n e -120-(TPP Dimer) Solvent 1 = Dichloromethane/TFA Solvent 2 = DMF Solvent 3 = Dichloromethane -121--122-(TPC Dimer) - 1 2 3 -- 1 2 4 -(TPBC Dimer) -125-- 1 2 6 -(ZnTPP Dimer) -127-1.0 Abs Q5H 7 0 0 R3 ( Z n T P C ) - 1 2 8 -- 1 2 9 -Abs *3 (ZnTPBC) - 1 3 0 -(ZnTPBC Dimer) 

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