4623
J . Am. Chem. Soc. 1987, 109, 4623-4626
A Temperature-, Multiplicity-, and Phase-Dependent Photorearrangement Sara Ariel, Syed H. Askari, John R. Scheffer,* James Trotter,* and Fred Wireko Contribution from the Department of Chemistry, University of British Columbia, Vancouver, Canada V6T 1 Y6. Received November 17, 1986 Abstract: The photochemistry of 2,3,4a,9a-tetramethyl-cis-4a,9a,9,1O-tetrahydro1,4-anthracenedione (1) has been found to be temperature-, multiplicity-, and phase-dependent. Direct irradiation at low temperatures in isotropic liquid phases gives predominantly photoproduct CP-3, whereas photolysis in solution at higher temperatures gives mainly CB-2. Sensitization/quenching studies show that 2 is triplet-derived and 3 is singlet-derived. From the linear plot of the natural logarithm of the 2/3 ratio vs. 1/T, the value of [E,(triplet) - E,(singlet)] is calculated to be 4.5 kcal/mol. Similar behavior was found for 2,3,4a,6,7,8a-hexamethyl-cis-4a,5,8,8a-tetrahydro-1,4-naphthalenedione (7). Photolysis of crystals of enedione 1 gives only product 2, regardless of the temperature employed. The X-ray crystal structure of 1 reveals the reasons for this specificity. An overall mechanistic scheme that explains both the solid state and solution results is presented and discussed.
The situation whereby a molecule reacts to give two products that are isomeric with the starting material is not uncommon in organic photochemistry, and it has been observed in many instances that the photoproduct ratio depends on some experimental variable in the photolysis procedure such as temperature,' phase change,2 or the presence of photosensitizers ( m ~ l t i p l i c i t y ) . ~It is rare, however, that a reaction is found in which all three of these factors come into play simultaneously, but we have discovered exactly such a case. This paper reports a photorearrangement that can be diverted in one direction by direct irradiation a t low temperatures in isotropic liquid phases and can be forced in a different direction by the use of higher temperatures and/or triplet energy photosensitizers (liquid phase) or by direct irradiation in the crystalline phase. T h e compound studied was 2,3,4a,9a-tetramethyI-cis4a,9a,9,10-tetrahydro-l,4-anthracenedione (1, Scheme I), mp 84-85 OC, prepared by the reaction between duroquinone and o - q ~ i n o d i m e t h a n e . ~Irradiation of this material in acetonitrile in a conventional immersion well apparatus using a 450-W Hanovia lamp fitted with a uranium glass filter (A > 330 nm) afforded mixtures of the cyclobutyl (CB) ketone 2 (96%) and the cyclopentyl (CP) ketone 3 (4%). Under the same conditions in methanol, the CB:CP ratio was 76:24. When the methanol irradiation was conducted in the presence of 1 molar equiv of benzophenone as a triplet energy sensitizer, cyclobutanone 2 became virtually the sole detectable product. This was corroborated by quenching studies using 2,5-dimethyl-2,4-hexadiene. The Stern-Volmer plot (Figure 1) shows that C B formation is quenched by the diene (k,r = 9.85 M-I) but that formation of the CP photoproduct is unaffected. As outlined in Scheme I, the C B photoproduct is formed via six-membered transition-state transfer of a benzylic hydrogen from C(10) to C(2) [or C(9) to C(3)] followed by C(3)-.C(10) [or C(2)-C(9)] bonding; CP is produced by five-membered transition (1) The photochemistry of dienes and trienes has been found to be generally temperature-dependent. For reviews, see: Dauben, W. G.; Kellogg, M. S.; Seeman, J . I.; Vietmeyer, N. D.; Wendschuh, P. H. Pure Appl. Chem. 1973, 33, 197. Dauben, W. G.; McInnis, E. L.; Michno, D. M. Rearrangements in Ground and Excited States; de Mayo, P., Ed.; Academic Press: New York, 1980; Vol. 3, Chapter 15. (2) For a review on the differences between unimolecular photorearrangements in solution and the crystalline state, see: Scheffer, J . R. Acc. Chem. Res. 1980, 13, 283. See, also: Appel, W. K.; Jiang, Z. Q , ;Scheffer, J. R.; Walsh, L. J . Am. Chem. SOC.1983, 105, 5354. (3) The photochemistry of &y-unsaturated ketones is generally multiplicity-dependent. For reviews, see: (a) Hixson, S. S.; Mariano, P. S.; Zimmerman, H. E. Chem. Rev. 1973, 73, 531. (b) Dauben, W. G.; Lodder, G.; Ipaktschi, J. Fortschr. Chem. Forsch 1975, 54, 73. (c) Houk, K. N. Chem. Reu. 1976, 76, 1. (d) Schaffner, K. Tetrahedron 1976, 32, 641. (e) Schuster, D. I. Rearrangements in Ground and Excited States; de Mayo, P., Ed.; Academic Press: New York, 1980; Vol. 3, pp 232-279. The di-rr-methane rearrangement is also multiplicity-dependent. For a review of this reaction, see: Zimmerman, H. E. Rearrangements in Ground and Excited States; de Mayo, P., Ed.; Academic Press: New York, 1980; Vol. 3, Chapter 16. (4) Askari, S.; Lee, S.; Perkins, R. R.; Scheffer, J. R. Can. J. Chem. 1985, 63, 3526.
0002-7863/87/ 1509-4623$01.50/0
Scheme I
1
CB-2
CP-3
Scheme I1
BR- 6
state abstraction by oxygen of a benzylic hydrogen atom [H(9) to O( 1) or H ( 10) to 0 ( 4 ) ] followed by C(3)--C(9) or C(2)-C( IO) bonding and ketonization of the resulting enol. Both processes have precedent in previous work from our l a b ~ r a t o r y . ~ In conducting the photolysis under different experimental conditions, we noted a puzzling variation in photoproduct ratio that could not be reconciled until we discovered that the process is temperature-dependent. Thus, as the temperature is lowered, the amount of product CP increases a t the expense of CB. The temperature dependence was studied quantitatively over the range -40 to f 2 0 OC by using a pulsed nitrogen laser (A = 337 nm) as the light source. When the data were plotted as In (CBICP) vs. 1 / T (Figure 2), a good straight line was obtained. This result is consistent with two competing first-order processes that have different activation energies, the slope of the straight line giving AE,. In the case of compound 1, [E,(CB) - E,(CP)] = 4.5 kcal/mol. Nitrogen laser irradiation of crystals of enedione 1 gave only C B photoproduct, regardless of the temperature used. In order to understand the reasons for this behavior, we determined the crystal and molecular structure of 1 by direct method X-ray diffraction studies. Crystals of 1 are monoclinic, space group Cc, a = 6.877 (2) A, b = 22.377 (3) A, c = 9.972 (3) A, p = 101.68 (l)', Z = 4. The structure was refined to a final R of 0.037 for 821 reflections with I > 3 4 0 . Full details will be published separately. Figure 3 is a stereo diagram of enedione 1 in its solid-state conformation. Both the enedione ring and the central ring are in approximate half-chair conformations. It is apparent from this ( 5 ) (a) Scheffer, J. R.; Bhandari, K. S.; Gayler, R. E.; Wostradowski, R. A. J. Am. Chem. SOC.1975, 97, 2178. (b) Scheffer, J. R.; Jennings, B. M.; Louwerens, J. P. J . Am. Chem. Sac. 1976, 98, 7040. (c) Scheffer, J. R.; Dzakpasu, A. A. J . Am. Chem. Sac. 1978, 100, 2163.
0 1987 American Chemical Society
4624 J . Am. Chem. SOC.,Vol. 109, No. 15, 1987
Ariel et al.
n
A
'9
Cyclobutanone 2 Cyclopentanone 3
N-
pigure 3. Stereodiagram showing solid-state conformation of enedione 1.
Scheme I11 e Y
Me& (D
-
,
,
,
I
,
0.1
0.0
I
0.4
,
,
,
a
,
, 1 .D
&$-I
,
Me
Me0
Me
M
Me&.: Me
Figure 1. Stern-Volmer quenching plot for enedione 1.
Me
Me0
7
Quencher Concentration ( M )
e
s
Me
CB-8
e Me
+
M
e
a
Me
.
Me
Me 0
Me 0
CP-9
EA-10
such processes.5c Why then is only CB photoproduct formed in the solid state? The answer is that the second step of the rearrangement, biradical closure, is permitted in the solid state for CB but not for CP. Closure to give CB occurs from a biradical (4, Scheme 11) that has the same conformation as the reactant 1. The C(3).-C(lO) distance in 1 is 3.13 A. In contrast, the initial biradical5 leading to C P is incapable of C(3)-C(9) bonding. The C(3)--C(9) distance (for 1) is 4.36 A. Thus formation of C P requires a half-chair to half-chair conformational isomerization of biradical 5 to biradical 6. This motion is too great to be accommodated by the crystal lattice, and so C P photoproduct is not observed in the solid state. No such restrictions exist in solution, however, and C P is formed in this medium. The C(3)-.C(9) distance in 6 may be approximated by the C(2)--C(lO) distance in 1, which is 3.31 A. A possible sequence of steps followed in the photorearrangement of 1 to CB and CP is shown below. The intermediacy of enol 3 (step 4) was verified by trapping in MeOD. It seems likely' that 1 (So)
1 (Si)
-
1 (S,)
& - k2
4
k-2
BR-5
(1) 1 (So)
(2)
k
BR-5 BR-6
k-3
BR-6
enol 3
CP-3
k4
5
I
I
0.3
I
I
0.35
I
[XIO-~
I
P4
I
I
0.45
I
1 (SI) I
l/Temperature (K) Figure 2. Temperature-dependence of photoproduct ratios.
conformation that CB and C P formation involve abstraction of different benzylic hydrogens. As outlined in Scheme 11, abstraction of Ha by C(2) leads to CB, and transfer of Hb to O( 1) gives CP. Both hydrogen-transfer processes are feasible geometrically. The H a 4 ( 2 ) distance is 2.75 A with 7, = 50.7' and A, = 74°.6 The Hb-.O(l) distance is 2.43 A, r0 = 2.7' and A. = 84.9°.6 These values lie well within the limits established for ~~
1 (TI) BR-4
1 (TI)
(3) (4)
71 (TI)
(5)
BR-4
(6)
CB-2
(7)
1 (So)
(8)
----+
k6
k7
the hydrogen abstraction processes (steps 2 and 6) are important contributors to A&, with step 2 having the lower activation energy, owing in part to the fact that S, has a higher excitation energy than TI8as well as to the greater resonance stabilization of bi-
~~
( 6 ) As illustrated below, T~ is the angle between the C(2)-H, vector and its projection on the plane of the C(2)-C(3) double bond; Ac is the C(3)-C(2)-H, angle. T,, is the angle between the O(l)-Hb vector and its projection on the plane of the carbonyl group; A, is the C(l)-O(l)-H, angle. substituents omitted
(7) Making the reasonable assumptions (for purposes of linearity of the Arrhenius plot) that k3
