:L'
J . Org. Chem. 1995,60,3919-3920
Efficient Preparation of the a,a&?-Atropoisomerof meso-Tetrakis(0-aminopheny1)porphyrin
3919
I
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Eric Rose,* Aurelien Cardon-Pilotaz, Melanie Quelquejeu, Nicolas Bernard, and Alain Kossanyi Lnboratoire de Chimie Organique. URA CNRS 408, Tour 44, 4 Place Jnssieu. 7.5230 Paris C e d a 05, France
*
60
50
Bernard Desmazikres
40 30 m
ERS CNRS 73, BBtiment F , Boite 45. 4 Place Jtmsieu, Lnboratoire de Chimie Organique Structurale 2, 75252 Paris C e d a 05. France Received February 15. 1995
Synthetic chiral porphyrins have attracted much interest as models for heme proteins.l;' The building blocks are usually achiral atropoisomeric meso-5,10,15,20-tetrakis(o-substituted pheny~)porphyrins~~h~ first superstructured Collman's "picket-fence" porphyrin is prepared from the pure a,a,a,a-atropoisomer of meso-tetrakis(2aminophenyUporphyrins, TAPPH2?x.h Then, "baskethandle",1J.4"pocket";" "picnic-basket" :Id gyroscope,'h.'.'J octopus,"" "twin-coronet",2cand many other porphyrins"b-' have been described. In most cases, the u,/f,a,P-TAPPH2 atropoisomer represents the starting material: its content in the atropoisomeric mixture under equilibrium is 111 la1 Gioves, J. T.; Myers. R. S.J.Am. Chmi. SOC.1983,10.5.5791. ibi Leeas. A,; L e v i d l e s . J.; Renko. 2.; Rase. E. Trtrahedro~zf x t f 1984. . 2 5 1.563. IC)Leeas. A,; Renko. Z.;Rose. E.Tdrahrdmn I M t . 1985.26, 1019. IdiMansuy, D.; Bnttioni. P.; Rcnaud. J.-P.;Guerin. P. J . C h e m Sm.,Chvm. C o m m u n 1985. 155. let Boitrel. B.; Lecas. A,; Renko. 2.; Rose. E. J . Chmn SM..( ' h e m . Commsn. 1985. 1820. In Ogoshi. H.; Saita, K.; Sakurai. K.; Watanahe. T.; Toi. H.; Aoyama, Y.; Okamoto. Y. Tdrahrdm,i Lett. 19Rfi. 27, 6365. 1g1Naruta. Y.; Mnruyama, K. Tetrahedron Let/. 1987. 28, 4 . i h ) Aayama. Y.; Saita, K.; Toi, H.: Ogoshi, H.; Okamoto. Y. T c t m h d m n I A t . 1987.2R. 4853. IiJ Groves. J. T.: Neumann, R. J . Am. ChPm S w 1987, IU9. 5045. ljl Boitrel. B.; Leeas, A,; Rose, E. Tetrahedron Lett. 1988, 29, 5653. IkJ Boitrel. B.; Lecas, A,: Renko. Z.; Rose, E. New J . C h w n . 1989. 13. 73. I l l Boitrel, 8.;Camilleri. E.; Fleche. Y.; Leeas,A,; Rose. E. Tvfmhedmn Left. 1989, 30, 29233. Iml Maillard. P.; Guerquin-Kern, J. L.: Momenteau. 11.; Gaspard. S. J . A m . Chem. S m 1989. 1 1 1 . 9125.1n)Boitrel.B.; Lecas. A.: Rose. E. J. Chem. Soc.. C h r m Commun. 1989. 349. lo1 Tetreau. C.: Boitrel, B.; Rose. E.; Lavalette, D. J . Chem. Soe., Chem. Commun. 1989. 1805. Ip)OMalley. S.: Kodadek.T.d.Am. Chrm. SOC.1989.111.
9116.
12Jlal Boitrel. B.; Lecas. A,; Rose. E. Tetrahedron Left. 1991. 32. 2129. IbJ Konishi. K.; Sugino, T.; Aida, T.; Inoue,S.J. Am. Chrm. Soc. 1991, 1 1 3 , 6487. le1 Naruta. Y.;Tani, F.; Ishihara. N.; Maruyama. K. J. Am. Chum Soc. 1991, 113. 6,865. Id1 Le Maux. P.; Bahri, H.; Simonneaux. G . J. Chwn Soe.. Chem. Commnn. 1991, 1350. le1 Maillard. P.; Huel. C.; Momenteau. M. Tefrahedmn Lett. 1992. 33. 80831. If) Boitrel. B.; Lecas. A,; Rose, E. Tetrahedrorz 1 ~ 4 1 .1992, 33. 227. Igl Le Maux, P.; Bnhri, H.; Simmoneaux. G . Tefrohedrwr 1993, 41). 1401. ihl Rose, E.; Boitrel. B.; Quelquejeu. M.; Kossanyi, A. TefrahedmnLett. 1993, 34, 7267. i i ) Kuroda. Y.; Kato. Y.; Higashioji, T.; Ogoshi, H. Anfies,. Chum.. frit. Ed. En#/.1993.32,723. IjI Maillard,
o o
in
0
zo a
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Figure 1. Thermal isomerization of the statistic ratio of crude TNPPZn at 120 "C. Table 1 Ratio of the Atropoisomers of TNPPZn in Naphthalene TPC) 110
n,/J.n,/i
n,n,iJ,ij
n,a,n,/j
7
76
15
2
120 145 160
13 23
92
6
68
19
42
35
n.n.n.n
only 12.5%. Recently, Nishino et aL6 and our group7" described the preparation of this isomer by thermal treatment of the meso-5,10,15,20-tetrakis(o-nitrophenyl~porphyrin atropoisomers TNPPH2 in toluene and naphthalene in 63.7%e and 72%'" abundances as determined by HPLC. In order to know if better results could be obtained, we undertook the same study with the Zn complexes of tetrakis(o-nitropheny1)porphyrinisomers, TNPPZn.4' Crude TNPPZnda (2g) and naphthalene (400 g) were heated at 120 "C under vigorous stirring for 4 days giving an homogeneous solution A. Unexpectedly, by analyzing the mixture by HPLC," we found that the a,a,b',fiatropoisomer was the major product (92%) and not the a,b,a,fione! (See Table 1and Figures 1and 2.) The hot solution A was poured into a concentrated HCI solution (400 mL) at -10 "C. CH2C12(11 at 0 "C) and SnClpQHrO (6.5 g)'h were slowly added, and the two-phase solution was magnetically stirred for 20h a t rt.? Naphthalene was removed in the CH2C12organic phase and could be recovered almost quantitatively (380 g). The HC1 phase
15) la) Komatsu. T.; Nakao, K.; Nishide, H.; Tsuehida, E. d. Chrm. Soe., Chem. Commun. 1993. 728. tbl Baldwin, J. E.: Perlmutter. P. Tap. Cur?. Chem. 1984,121. 181.lel Osuka. A,; Nagata. T.; Maruyama, K. Chem. Letf. 1991. 1687. Id) Nagata. T. B d l . Chrm. Scx. J p n . 1992, 6 5 . 385. l e ) Collman, J. P.; Zhang. X.; Herrmann. P. C.; Uflelman. E. S.; Boitrel. B.: Stmumanis. A,; Brauman. J. 1. J . Am. Chem. Soc. 1994. I l f i . 2fiRI. See also some articles described in references 1 and 2. hut of course this list i s not exhaustive! l3)iaJCollmnn.J.P.;Gape.R.R.;Reed.C.A.;H;~lbert.T.R.;Lang. (61Nishino, N.; Kobata. K.; Mihara. H.: Fujimoto, T. Chrm. Le//. 1992, 1991. G . ; Robinson. W. T.J . Am. C h u m Soc. 1975. 97, 1427. Ib) Sorrell. T. 171lal Rose. E.; Quelquejeu, M.; Pochet. C.: Julie", N.; Kossanyi, N. htnrpmir Svnlhrsis: MeGraw-Hill: New York. 19x0: Vol. XX. p 161. le1 Collman. J. P.; Brauman. J . 1.: Collins, T. J.: Iveraon, B. L.: Lang, A,: Hamon, L. J . Org. Chem. 1993.58,5030. IbJLeeas, A,; Boitrel, B.: Rose. E. Bull. Sac. Chim. Fr. 1991. 128. 407. G.;Pettman. R. B.; Sessler, J . L.; Walters. M. A. J . A m . Chem. Soc. 18) a./J,n./J-Atropoisomer. t = 10.48 min; a.a.n,iJ-atropoisomer, t = 1983. 10.5. 3038.Id1 Collman. J. P.; Brauman, J. 1.; Fitzgerald. J. P.; 11.04 min; n,n./J./J-ati0p(lisl)mer, f = 13.46 min; a.n.R.n-at10p01SOme1. Hampton. P. D.; Naruta, Y.: Sparapany.d. W.; Ibers,J. A. J. Am. Chem. t =13.98 mi"; column cyano-bonded silica: internal diameter = 4.6 mm. Soc 1988. 110. 3477. 1 = 300 m m ;d p = IO flow l a t e 1 mWmin; eluent 25-45% THF/ 1411:~Mamentenu. M.; Mirpelter, J.: h o c k . B.; Lhoste. J. M. J. heptane for 15 mi"; detection W - v i s , 420 nm: injections. I O ,rL of Chrm. Sor., Pvrkin Trans. I 1985, 221. ihl Staubli, B.; Fretr, H.: the mixture dissolved in acetone. Piantini. U.; Woggon. W. D. H d v C h i m A d o 1987. 70. 1173.
P.; Guerquin-Kern. J. L.; Huel, C.; Momenteau, M. J . O w Chem 1993. 68,2774. IkJCollman. J. P.; Zhang, X.; h e . V. J.: Uffelmnn. E. S.; Brauman. J. 1. Science 1993, 2fil. 1404. ill Mizutani, T.; Ema, 'T.; Tomita. T.; Kuroda, Y.; Ogoshi. H. J . Chem. Soe.. Chem. Commun. 1993.520. ( m l Kanishi. K.: Yahara, K.; Toshishige, H.; Aida. T.; Inoue. S. J. Am. Chem. SOC.1994. I l f i . 1337. In1 Le M a w P.; Bahri. H.; Simonneaux. G . J. Chem. Soc.. C h e m Corm". 1994. 1287.
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0022-3263/95/1960-3919$09.00/0 0 1995 American Chemical Society
3920 J. Org. Chem., Vol. 60, No. 12, 1995 O;,f
u-
TNPPZn
Figure 2.
was extracted twice with 100 mL of CHzClz and neutralized slowly with NH40H until neutral pH. After five extractions (5 x 250 mL CHzClZ) and finally another one with magnetic stirring for one night, the combined organic phases were dried over MgS04, evaporated under reduced pressure, and chromatographed on silica gel (15 pm) with CHzClz and ether (60l40). The meso-a,a,P,/?tetrakido-aminopheny1)porphyrin atropoisomer (TAPPHz) was precipitated by adding petroleum ether to the CHzClz solution to give 804 mg (63% yield). At 160 "C and a t 145 "C in naphthalene, 42% and 68% of the a,a,P,P-TNPPZn isomer were respectively obtained as observed by HPLC study (Table 1). At 110 "C, 76% of this isomer was observed. At the same temperature, crude TNPPZn was refluxed for 7 days in toluene but only 35% of the a,a,p,p-isomer was formed; this shed light on the crucial role of the naphthalene. In the case of the free base TNPPHz a t 130 "C in naphthalene, 72% of the a,p,a,p-atropoisomer was determined by HPLC afker only 20 min,7a and such a ratio cannot be obtained in xylene for example.
Notes The statistic ratio 1/1/214 = a&$/aaaa/a4BP/aaa/3 of crude TNPPHz and of TAPPHz are recovered by condensation of pyrrole and o-nitrobenzaldehyde and also after the reduction of the nitro isomers.3a The a,a,a,P nitro derivative represents the more abundant product. The a,a,a,a-isomer has been obtained as the major one by Elliottga and Lindseygbby treating the mixture in silica gel. The atropoisomerization of the mixture in toluene or naphthalene readily gives principally the a,p,a,pi s ~ m e r . Finally, ~ , ~ ~ we describe the obtention of the last ( u s e f ~ 1 ) atropoisomer, ~ g ~ ~ ~ ~ ~ a,a,P,P, by appropriate rotation of the other isomers of the TNPPZn mixture a t 120 "C in naphthalene for 4 days followed by reduction a t rt. The reasons for the high relative yield of the a,a,@,Patropoisomer are currently unknown.1° Work is in progress to elucidate such recognition of one atropoisomer to gain an insight of this process. 509502920 (9)(a) Elliott, C. M. Anal. Chem. 1980,52,660. (b) Lindsey, J.J. Org. Chem. 1980,45, 5215.Momenteau et al. obtained an a,a,a,aatropoisomer in the case of meso-tetrakis(2,3,4,6-tetraacetyl-O-Pglucosylpheny1)porphyrin by treating also the mixture of isomers in the presence of silica geLgC(c) Maillard, P.; Vilain, S.; Huel, C.; Momenteau, M. J . Org. Chem. 1994,59,2887. Hayashi and Ogoshi et al. described also a shift of another equilibrium of atropoisomers to the a,a,a,a-isomer in homogeneous solution.gd(d) Hayashi, T.; Asai, T.; Hokazono, H.; Ogoshi, H. J . Am. Chem. Soc. 1993,115, 12210. (10)The 926 abundance could be interpreted by a stabilization of two nitro groups by a polar water molecule and/or by ligation of the Zn complex by a water molecule which could favor the a,a,P,Patropoisomer by means of hydrogen bonds. In order to prove it, a,a,P,PTNPPZn was crystallized in a mixture of CHZC12 and pentane, but unfortunately, the cristals did not diffract yet and in solution 'H NMR study did not show a water molecule signal.
