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The Conservation of Orbital Symmetry†
Prof. R. B. Woodward,
Prof. Roald Hoffmann,
Corresponding Author
Prof. R. B. Woodward
Department of Chemistry, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138 (USA)
R. B. Woodward, Department of Chemistry, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138 (USA)
Roald Hoffmann, Department of Chemistry, Cornell University, Ithaca, New York 14850 (USA)
Search for more papers by this authorCorresponding Author
Prof. Roald Hoffmann
Department of Chemistry, Cornell University, Ithaca, New York 14850 (USA)
R. B. Woodward, Department of Chemistry, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138 (USA)
Roald Hoffmann, Department of Chemistry, Cornell University, Ithaca, New York 14850 (USA)
Search for more papers by this authorProf. R. B. Woodward,
Prof. Roald Hoffmann,
Corresponding Author
Prof. R. B. Woodward
Department of Chemistry, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138 (USA)
R. B. Woodward, Department of Chemistry, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138 (USA)
Roald Hoffmann, Department of Chemistry, Cornell University, Ithaca, New York 14850 (USA)
Search for more papers by this authorCorresponding Author
Prof. Roald Hoffmann
Department of Chemistry, Cornell University, Ithaca, New York 14850 (USA)
R. B. Woodward, Department of Chemistry, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138 (USA)
Roald Hoffmann, Department of Chemistry, Cornell University, Ithaca, New York 14850 (USA)
Search for more papers by this author†
This memoir will also be published as a separate brochure, copies of which can be ordered from Verlag Chemie GmbH, D-694 Weinheim, Postfach 129/149 (Germany), Academic Press Inc., 111 Fifth Avenue, New York, N.Y. 10003 (USA), or Academic Press Inc. Ltd., Berkeley Square House, Berkeley Square, London W. 1 (England), at a price of ca. DM 16.– or $ 4.40. A German version is also available from Verlag Chemie GmbH.
References
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- 5In addition to the classical text by
C. A. Coulson
( Valence. 2nd ed.,
Oxford University Press, London
1961),
we recommend:
C. A. Coulson and
E. T. Stewart in
S. Patai:
The Chemistry of Alkenes.
Wiley-Interscience, New York
1964,
E. Heilbronner and
H. Bock:
Das HMO-Modell und seine Anwendung.
Verlag Chemie, Weinheim
1968,
and
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- 6Throughout this paper molecular orbitals are symbolized in terms of the atomic orbitals whose interaction gives the actual molecular orbital; since we are in general interested only in nodal properties, we ignore the fact that the coefficients – and thus the relative sizes – of the resultant atomic orbital contributions are not all identical.
- 7The electronic structure of polyenes is perhaps the most highly developed branch of semi-empirical molecular orbital theory. A very good survey of the field is given in L. Salem: The Molecular Orbital Theory of Conjugated Systems. Benjamin, New York 1966. See also A. Streitwieser: Molecular Orbital Theory for Organic Chemists. Wiley, New York 1961.
- 8 F. Hund, Z. Phys. 40, 742 (1927); Z. Phys. 42, 93 (1927); Z. Phys. 51, 759 (1928); R. S. Mulliken, Phys. Rev. 32, 186 (1928); Rev. Mod. Phys. 4, 1 (1932). See also G. Herzberg: The Electronic Structure of Diatomic Molecules. 2nd edition, Van Nostrand, Princeton 1950.
- 9We could, of course, label the levels with their proper symmetry designations, appropriate to the D2h symmetry of the approach. We deliberately use the symmetric (S) and antisymmetric (A) labels since the nodal properties of the orbitals are then most clearly discernible.
- 10The rule follows directly from perturbation theory and the correlation of higher energy with increasing number of nodes in a wave function.
- 11A similar situation arises in other areas of chemistry. The n→π* transition in formaldehyde is electric-dipole forbidden. The source of the small intensity observed is still disputed. In the cases of acetaldehyde, or of unsymmetrically substituted ketones, the symmetry element which made the formaldehyde transition electric-dipole forbidden is removed. The transition becomes allowed. Does it therefore jump to a high intensity? Not at all; the intensity remains practically unchanged. This is because the essential symmetry, that of the local environment of the carbonyl group, is unchanged.
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P. v. R. Schleyer,
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E. E. van Tamelen and
T. L. Burkoth,
J. Amer. chem. Soc.
89, 151
(1967).
Related cases were studied by
R. C. Cookson,
J. Hudec, and
J. Marsden,
Chem. Ind.
1961, 21,
and by
E. Vogel,
W. Meckel, and
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- 70Similar conclusions have been reached by Wiberg on the basis of semi-empirical MO calculations [ K. B. Wiberg, Tetrahedron 24, 1083 (1968)].
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- 78For example, G. S. Hammond, N. J. Turro, and R. S. H. Liu, J. org. Chem. 28, 3297 (1963); G. S. Hammond and R. S. H. Liu, J. Amer. chem. Soc. 85, 477 (1963); D. Valentine, N. J. Turro, and G. S. Hammond, J. Amer. chem. Soc. 86, 5202 (1964); R. S. H. Liu, N. J. Turro, and G. S. Hammond, J. Amer. chem. Soc. 87, 3406 (1965); G. O. Schenck, S.-P. Mannsfeld, G. Schomburg, and C. H. Krauch, Z. Naturforsch. 19b, 18 (1964).
- 79
J. Meinwald and
P. H. Mazzocchi,
J. Amer. chem. Soc.
88, 2850
(1966);
J. Meinwald,
A. Eckell, and
K. L. Erickson,
J. Amer. chem. Soc.
87, 3532
(1965);
H. Prinzbach and
H. Hagemann,
Angew. Chem.
76, 600
(1964);
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R. Criegee and
R. Askani,
Angew. Chem.
80, 531
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- 105(a) Two recent reviews serve as excellent guides to the elegant structural work accomplished. K. Schaffner, Advances in Photochemistry 4, 81 (1966); (b) P. J. Kropp, Organic Photochemistry 1, 1 (1967).
- 106 D. H. R. Barton, J. McGhie, and R. Rosenberger, J. chem. Soc. 1961, 1215; D. H. R. Barton, P. de Mayo, and M. Shafiq, J. chem. Soc. 1958, 140, 3314; D. Arigoni, H. Bosshard, H. Bruderer, G. Büchi, O. Jeger, and L. J. Krebaum, Helv. chim. Acta 40, 1732 (1957) and other papers referred to in ref. [105].
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H. E. Zimmerman,
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1, 183
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H. E. Zimmerman,
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D. I. Schuster,
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- 113Only the consequences of an addition on the double bond next to R are sketched. Of course the addition on the opposite side is feasible, and will double the number of possible products.
- 114 D. I. Schuster, personal communication.
- 115 H. Dutler, M. Bosshard, and O. Jeger, Helv. chim. Acta 40, 494 (1957); K. Weinberg, E. C. Utzinger, D. Arigoni, and O. Jeger, Helv. chim. Acta 43, 236 (1960); H. Dutler, C. Ganter, H. Ryf, E. C. Utzinger, K. Weinberg, K. Schaffner, D. Arigoni, and O. Jeger, Helv. chim. Acta 45, 2346 (1962); C. Ganter, F. Greuter, D. Kägi, K. Schaffner, and O. Jeger, Helv. chim. Acta 47, 627 (1964); F. Frei, C. Ganter, D. Kägi, K. Kocsis, M. Miljković, A. Siewinski, R. Wenger, K. Schaffner, and O. Jeger, Helv. chim. Acta 49, 1049 (1966).
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- 117 D. Belluš, D. R. Kearns, and K. Schaffner, Helv. chim. Acta 52, 971 (1969).
- 118 J. R. Williams and H. Ziffer, Chem. Commun. 1967, 194, 469; Tetrahedron 24, 6725 (1968).
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- 120 G. W. Griffin, J. Covell, R. C. Petterson, R. M. Dodson, and G. Klose, J. Amer. chem. Soc. 87, 1410 (1965); H. Kristinsson and G. W. Griffin, J. Amer. chem. Soc. 88, 378 (1966).
- 121 H. E. Zimmerman and K. G. Hancock, J. Amer. chem. Soc. 90, 3749 (1968). See also H. E. Zimmerman and R. L. Morse, J. Amer. chem. Soc. 90, 954 (1968).
- 122 E. Pfenninger, D. E. Poel, C. Berse, H. Wehrli, K. Schaffner, and O. Jeger, Helv. chim. Acta 51, 772 (1968).
- 123 R. R. Sauers and A. Shurpik, J. org. Chem. 33, 799 (1968).
- 124 W. R. Roth and B. Peltzer, Liebigs Ann. Chem. 685, 56 (1965).
- 125 J. R. Edman, J. Amer. chem. Soc. 88, 3454 (1966).
- 126 E. Ciganek, J. Amer. chem. Soc. 88, 2882 (1966).
- 127 H. E. Zimmerman, R. S. Givens, and R. M. Pagni, J. Amer. chem. Soc. 90, 4192 (1968). See also J. P. N. Brewer and H. Heaney, Chem. Commun. 1967, 811; P. W. Rabideau, J. B. Hamilton, and L. Friedman, J. Amer. chem. Soc. 90, 4465 (1968).
- 128 H. E. Zimmerman, R. W. Binkley, R. S. Givens, and M. A. Sherwin, J. Amer. chem. Soc. 89, 3932 (1967).
- 128aSince the above was written, this prediction has received elegant experimental confirmation: J. A. Berson and S. S. Olin, J. Amer. chem. Soc. 91, 777 (1969).
- 129Inter alia: A. T. Blomquist and Y. C. Meinwald, J. Amer. chem. Soc. 81, 667 (1959); R. C. Cookson, S. S. H. Gilani, and I. D. R. Stevens, Tetrahedron Letters 1962, 615; H. K. Hall, J. org. Chem. 25, 42 (1960).
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- 132
C. D. Smith,
J. Amer. chem. Soc.
88, 4273
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Cf. also
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Pure appl. Chem.
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J. F. M. Oth,
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10.1002/ange.19680801538 Google ScholarAngew. Chem. internat. Edit. 7, 646 (1968); Rec. Trav. chim. Pays-Bas 87, 1185 (1968).
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H. Prinzbach,
M. Arguëlles, and
E. Druckrey,
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- 137 C. Steel, R. Zand, P. Hurwitz, and S. G. Cohen, J. Amer. chem. Soc. 86, 679 (1964).
- 138 R. Askani, Chem. Ber. 98, 3618 (1965).
- 139 M. Takahashi, Y. Kitahara, I. Murata, T. Nitta, and M. C. Woods, Tetrahedron Letters 1968, 3387.
- 140 H. C. Longuet-Higgins in: Theoretical Organic Chemistry. The Kekulé Symposium. Butterworths, London 1959, p. 17.
- 141For example, [1−14C]-propylene does not rearrange to [3−14C]-propylene: B. Sublett and N. S. Bowman, J. org. Chem. 26, 2594 (1961).
- 142 J. A. Berson and G. L. Nelson, J. Amer. chem. Soc. 89, 5303 (1967); J. A. Berson, Accounts Chem. Res. 1, 152 (1968).
- 143 W. J. Bailey and R. A. Baylouny, J. org. Chem. 27, 3476 (1962).
- 144 W. von E. Doering, personal communication; cf. E. F. Ullman, J. Amer. chem. Soc. 82, 505 (1960).
- 145 C. G. Overberger and A. E. Borchert, J. Amer. chem. Soc. 82, 1007 (1960).
- 146 M. C. Flowers and H. M. Frey, J. chem. Soc. 1961, 3547, R. J. Ellis and H. M. Frey, J. chem. Soc. 1964, 959, 4188; C. J. Elliot and H. M. Frey, J. chem. Soc. 1965, 345; J. chem. Soc. A, 1966, 553; C. A. Wellington, J. physic. Chem. 66, 1671 (1962); H. M. Frey and D. C. Marshall, J. chem. Soc. 1962, 3981; G. R. Branton and H. M. Frey, J. chem. Soc. 1966, 1342.
- 147 B. S. Rabinowitch, E. W. Schlag, and K. B. Wiberg, J. chem. Physics 28, 504 (1958); B. S. Rabinowitch and E. W. Schlag, J. Amer. chem. Soc. 86, 5996 (1960).
- 148 K. W. Egger, D. M. Golden, and S. W. Benson, J. Amer. chem. Soc. 86, 5420 (1964).
- 149 M. R. Willcott and V. M. Cargle, J. Amer. chem. Soc. 89, 723 (1967); W. R. Roth, personal communication.
- 150 W. G. Dauben and W. T. Wipke, Pure appl. Chem. 9, 539 (1964). J. J. Hurst and G. M. Whitham, J. chem. Soc. 1960, 2864; R. C. Cookson, V. N. Gogte, J. Hudec, and N. A. Mirza, Tetrahedron Letters 1965, 3955; W. F. Erman and H. C. Kretschmar, J. Amer. chem. Soc. 89, 3842 (1967); R. F. C. Brown, R. C. Cookson, and J. Hudec, Tetrahedron 24, 3955 (1968); R. C. Cookson, Chemistry in Britain 5, 6 (1960); E. Baggiolini, H. P. Hamlow, K. Schaffner, and O. Jeger, Chimia 23, 181 (1969).
- 151References to the literature may be found in D. S. Glass, R. S. Boikess, and S. Winstein, Tetrahedron Letters 1966, 999. An interesting recently discovered [1,5] shift of a methyl group is described by R. Grigg, A. W. Johnson, K. Richardson, and K. W. Shelton, Chem. Commun. 1967, 1192; cf. also V. Boekelheide and E. Sturm, J. Amer. chem. Soc. 91, 902 (1969).
- 152 W. R. Roth and J. König, Liebigs Ann. Chem. 699, 24 (1966). See also H. Kloosterziel and A. P. ter Borg, Rec. Trav. Chim. Pays-Bas 84, 1305 (1965).
- 153 W. R. Roth and J. König, personal communication.
- 154 V. A. Mironov, E. V. Sobolev, and A. N. Elizarova, Tetrahedron 19, 1939 (1963); S. McLean and R. Haynes, Tetrahedron Letters 1964, 2385.
- 155 W. R. Roth, Tetrahedron Letters 1964, 1009.
- 156
A. P. ter Borg,
H. Kloosterziel, and
N. van Meurs,
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82, 717, 741, 1189
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10.1002/recl.19630820712 Google ScholarE. Weth and A. S. Dreiding, Proc. chem. Soc. 1964, 59; K. W. Egger, J. Amer. chem. Soc. 89, 3688 (1967).
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- 158 W. R. Roth, Liebigs Ann. Chem. 671, 25 (1964).
- 159For example: R. Srinivasan, J. Amer. chem. Soc. 84, 3982 (1962); K. J. Crowley, Proc. chem. Soc. 1964, 17; H. Prinzbach and E. Druckrey, Tetrahedron Letters 1964, 2959.
- 160 E. F. Zwicker, L. I. Grossweiner, and N. C. Yang, J. Amer. chem. Soc. 85, 2671 (1963); G. Wettermark, Photochem. Photobiol. 4, 621 (1965); K. R. Huffman, M. Loy, and E. F. Ullman, J. Amer. chem. Soc. 87, 5417 (1965); G. Büchi and N. C. Yang, J. Amer. chem. Soc. 79, 2318 (1957).
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- 163 T. Miyashi, M. Nitta, and T. Mukai, Tetrahedron Letters 1967, 3433.
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A. P. ter Borg and
H. Kloosterziel,
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84, 241
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- 166a R. Hug, H.-J. Hansen, and H. Schmid, Chimia 23, 108 (1969).
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- 168 Gy. Fráter and H. Schmid, Helv. chim. Acta 51, 190 (1968).
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- 170 D. A. McCaulay and A. P. Lien, J. Amer. chem. Soc. 79, 5953 (1957); H. Steinberg and F. L. J. Sixma, Rec. Trav. Chim. Pays-Bas 81, 185 (1962); C. MacLean and E. L. Mackor, J. chem. Physics 34, 2208 (1961); V. A. Koptyug, V. G. Shubin, and A. I. Rezvukhin, Izv. Akad. Nauk SSSR 1965, 201.
- 171 D. W. Swatton and H. Hart, J. Amer. chem. Soc. 89, 5075 (1967).
- 172 T. M. Brennan and R. K. Hill, J. Amer. chem. Soc. 90, 5614 (1968).
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- 174 H. Hart, T. R. Rodgers, and J. Griffiths, J. Amer. chem. Soc. 91, 754 (1969).
- 175 R. F. Childs and S. Winstein, J. Amer. chem. Soc. 90, 7146 (1968).
- 176 H.-J. Hansen, B. Sutter, and H. Schmid, Helv. chim. Acta 51, 828 (1968).
- 177 Y. Makisumi and S. Notzumoto, Tetrahedron Letters 1967, 6393.
- 178 U. Schöllkopf and K. Fellenberger, Liebigs Ann. Chem. 698, 80 (1966). See also H. E. Zimmerman in P. de Mayo: Molecular Rearrangements. Interscience, New York 1963, Vol. 1, p. 372.
- 179 J. E. Baldwin, R. E. Hackler, and D. P. Kelly, Chem. Commun. 1968, 537, 538; G. M. Blackburn, W. D. Ollis, J. D. Plackett, C. Smith, and I. O. Sutherland, Chem. Commun. 1968, 186; R. B. Bates and D. Feld, Tetrahedron Letters 1968, 417; B. M. Trost and R. La Rochelle, Tetrahedron Letters 1968, 3327; J. E. Baldwin and R. E. Peavy, Tetrahedron Letters 1968, 5029; W. Kirmse and M. Kapps, Chem. Ber. 101, 994, 1004 (1968).
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J. H. Brewster and
M. W. Kline,
J. Amer. chem. Soc.
74, 5179
(1952);
B. J. Millard and
T. S. Stevens,
J. chem. Soc.
1963, 3397;
E. F. Jenny and
J. Druey,
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- 184 D. S. Glass, J. Zirner, and S. Winstein, Proc. chem. Soc. 1963, 276; R. J. Ellis and H. M. Frey, Proc. chem. Soc. 1964, 221; J. chem. Soc. 1964, Suppl. 1, 5578; W. R. Roth, Liebigs Ann. Chem. 671, 10 (1964); W. R. Roth and J. König, Liebigs Ann. Chem. 688, 28 (1965); W. Grimme, Chem. Ber. 98, 756 (1965); J. K. Crandall and R. J. Watkins, Tetrahedron Letters 1967, 1717; R. M. Roberts, R. G. Landolt, R. N. Greene, and E. W. Heyer, J. Amer. chem. Soc. 89, 1404 (1967); G. Ohloff, Tetrahedron Letters 1965, 3795; W. R. Roth, Chimia 20, 229 (1966). – The reaction is also known in the case of cyclopropyl-carbonyl compounds: D. E. McGreer, N. W. K. Chiu, and R. S. McDaniel, Proc. chem. Soc. 1964, 415. A special case of some interest is the “abnormal Claisen rearrangement” studied by E. N. Marvell, D. R. Anderson, and J. Ong, J. org. Chem. 27, 1109 (1962); W. M. Lauer and T. A. Johnson, J. org. Chem. 28, 2913 (1963); A. Habich, R. Barner, W. von Philipsborn, and H. Schmid, Helv. chim. Acta 48, 1297 (1964); R. M. Roberts and R. G. Landolt, J. Amer. chem. Soc. 87, 2281 (1965); R. M. Roberts, R. N. Greene, R. G. Landolt, and E. W. Heyer, J. Amer. chem. Soc. 87, 2282 (1965); R. M. Roberts, R. G. Landolt, R. N. Greene, and E. W. Heyer, J. Amer. chem. Soc. 89, 1404 (1967). See also J. M. Conia, F. Leyendecker, and C. Dubois-Faget, Tetrahedron Letters 1966, 129; F. Rouessac and J. M. Conia, Tetrahedron Letters 1965, 3313.
- 185Reviewed by S. Hünig, H. R. Müller, and W. Thier, Angew. Chem. 77, 368 (1965); Angew. Chem. internat. Edit. 4, 271 (1965); E. J. Corey, D. J. Pasto, and W. L. Mock, J. Amer. chem. Soc. 83, 2957 (1961).
- 186 W. von E. Doering and J. W. Rosenthal, J. Amer. chem. Soc. 89, 4535 (1967).
- 187 P. Dowd, personal communication; I. Fleming, personal communication.
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- 189 W. Reusch, M. Russell, and C. Dzurella, J. org. Chem. 29, 2446 (1964).
- 190 J. E. Baldwin, Tetrahedron Letters 1966, 2953.
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K. Alder and
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P. S. Skell and
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J. Amer. chem. Soc.
81, 3383
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P. S. Skell and
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