The Role of Aromatic Radical Cations and Benzylic Cations in the 2,4,6-Triphenylpyrylium Tetrafluoroborate Photosensitized Oxidation of Ring-Methoxylated Benzyl Alcohols in CH2Cl2 Solution Barbara Branchi,1a Massimo Bietti,*,1a Gianfranco Ercolani,1a M. Angeles Izquierdo,1b Miguel A. Miranda,1b and Lorenzo Stella1a Dipartimento di Scienze e Tecnologie Chimiche, Universita` “Tor Vergata”, Via della Ricerca Scientifica, I-00133 Rome, Italy, and Departamento de Quı´mica, Instituto de Tecnologı´a Quı´mica UPV-CSIC, Universidad Polite´ cnica de Valencia, Camino Vera s/n, Apdo. 22012, 46022 Valencia, Spain
[email protected] Received August 19, 2004
A steady-state and laser flash photolysis (LFP) study of the TPPBF4-photosensitized oxidation of ring-methoxylated benzyl alcohols has been carried out. Direct evidence on the involvement of intermediate benzyl alcohol radical cations and benzylic cations in these reactions has been provided through LFP experiments. The reactions lead to the formation of products (benzaldehydes, dibenzyl ethers, and diphenylmethanes) whose amounts and distributions are influenced by the number and relative position of the methoxy substituents. This behavior has been rationalized in terms of the interplay between the stabilities of benzyl alcohol radical cations and benzyl cations involved in these processes. A general mechanism for the TPPBF4-photosensitized reactions of ringmethoxylated benzyl alcohols has been proposed, where the R-OH group of the parent substrate acts as the deprotonating base promoting R-C-H deprotonation of the benzyl alcohol radical cation (formed after electron transfer from the benzyl alcohol to TPP*) to give a benzyl radical and a protonated benzyl alcohol, precursor of the benzylic cation. This hypothesis is in contrast with previous studies, where formation of the benzyl cation was suggested to occur from the neutral benzyl alcohol through the Lewis acid action of excited TPP+ (TPP*). 2,4,6-Triarylpyrylium salts are easily photoexcited by visible light, and the photosensitizing ability of these species has been widely applied in photoinduced electron transfer (PET) processes. Among these salts, 2,4,6triphenylpyrylium tetrafluoroborate (TPPBF4) has received most attention.2 TPPBF4 is a very strong oxidant in both the singlet and triplet excited state, able to oxidize several organic donors (D) to the corresponding radical cations (D•+) with concomitant formation of the triphenylpyranyl radical, TPP• (Scheme 1). The neutral character of TPP• reduces the importance of the competing back-electron-transfer (BET) process, thus favoring the followup reactions of D•+. Very importantly, since TPP+ may be regenerated through the reaction of TPP• with O2, photooxidation processes can be usually carried out in air or O2-saturated solution using catalytic amounts of TPP+. It has been shown that in acetonitrile or dichloromethane solution the TPPBF4-photosensitized reaction (1) (a) Universita` “Tor Vergata”. (b) Universidad Polite´cnica de Valencia. (2) See, for example: (a) Miranda, M. A.; Garcia, H. Chem. Rev. 1994, 94, 1063-1089. (b) Sanjuan, A.; Pillai, M. N.; Alvaro, M.; Garcia, H. Chem. Phys. Lett. 2001, 341, 153-160. (c) Akaba, R.; Iwasaki, M.; Matsumura, T.; Kamata, M.; Itoh, H. J. Phys. Org. Chem. 1996, 9, 187-190. (d) Akaba, R.; Kamata, M.; Sakuragi, H.; Tokumaru, K. Tetrahedron Lett. 1992, 33, 8105-8108. (e) Akaba, R.; Sakuragi, H.; Tokumaru, K. J. Chem. Soc., Perkin Trans. 2 1991, 291-297.
SCHEME 1
SCHEME 2
of ring-substituted benzyl alcohols proceeds through two different pathways depending on the nature of the ring substituent.3 With benzyl and 4-chlorobenzyl alcohol, formation of the corresponding benzaldehyde has been observed. This result has been explained in terms of the formation of an intermediate aromatic radical cation followed by deprotonation (Scheme 2), a typical reaction of benzyl alcohol radical cations.4,5 No oxidation products have been instead observed when 4-methoxybenzyl alcohol (1) has been reacted under (3) Martiny, M.; Steckhan, E.; Esch, T. Chem. Ber. 1993, 126, 16711682. (4) Baciocchi, E.; Bietti, M.; Lanzalunga, O. Acc. Che. Res. 2000, 33, 243-251. 10.1021/jo048546h CCC: $27.50 © 2004 American Chemical Society
8874
J. Org. Chem. 2004, 69, 8874-8885
Published on Web 11/10/2004
Oxidation of Ring-Methoxylated Benzyl Alcohols SCHEME 3
CHART 1
the same experimental conditions, the reaction leading to bis(4-methoxybenzyl) ether (1a), 4,4′-dimethoxydiphenylmethane (1b), and [4-methoxy-3-(4-methoxybenzyl)phenyl](4-methoxyphenyl)methane (1c). This behavior has been explained in terms of excited TPP+ (TPP*) acting as a Lewis acid catalyst promoting the formation of an intermediate 4-methoxybenzyl cation from which, following different pathways, products 1a-c can be formed (Scheme 3; An ) 4-MeOC6H4).3 The change in mechanism observed on going from benzyl and 4-chlorobenzyl alcohol to 4-methoxybenzyl alcohol (1) has been thus attributed to the greater stability of the 4-methoxybenzyl cation as compared to the benzyl and 4-chlorobenzyl ones: no radical cation intermediate is formed in the reaction of 1 even though 1•+ is expected to be significantly more stable than both benzyl alcohol and 4-chlorobenzyl alcohol radical cations.6,7 Along this line, in view of our continuing interest on the one-electron oxidation of ring methoxylated arylalkanols, and in order to gain additional information on the mechanism of the TPPBF4-photosensitized oxidation of benzyl alcohols, and in particular on the eventual role of aromatic radical cations and benzylic cations in this process, we have carried out a detailed steady-state and laser flash photolysis (LFP) study of the TPPBF4-photosensitized reaction of 4-methoxybenzyl alcohol (1) and of some structurally related substrates (1a, 2-11) whose structures are shown in Chart 1. Additional information comes from the results of DFT calculations for the determination of the relative stabilities of ring-methoxylated benzyl cations, carried out at the B3LYP/6-31G(d) level of theory. Results Steady-State Photolysis. In a typical experiment, air- or O2-saturated CH2Cl2 solutions (10 mL) at T ) 25 °C, containing TPPBF4 (5 × 10-4 M) and the substrate (5) Baciocchi, E.; Bietti, M.; Steenken, S. Chem. Eur. J. 1999, 5, 1785-1793. (6) Yasuda, M.; Nakai, T.; Kawahito, Y.; Shiragami, T. Bull. Chem. Soc. Jpn. 2003, 76, 601-605. (7) Fukuzumi, S.; Kochi, J. K. J. Am. Chem. Soc. 1981, 103, 72407252.
(1, 1a, 2-8, 10: 2.5-5 × 10-3 M), were irradiated at λ ) 365 nm (10 × 15 W lamps) for times varying between 1 and 60 min. After workup, the reaction products were identified by 1H NMR and GC-MS (comparison with authentic samples). Unreacted substrate and reaction products were quantitatively determined by GC in the presence of an internal standard (1,2-diphenylethane). Good to excellent mass balances (g85%) were obtained in all experiments. The product distributions obtained in the TPPBF4photosensitized reactions of 1 are collected in Table 1. Some experiments were also carried out in the presence of a cosensitizer such as biphenyl (BP) (entry 3) or of a base such as pyridine (entries 4, 7, and 10-12) or 1,2epoxybutane (entries 5, 8, 13, and 14). In the absence of added base, fast consumption of 1 is observed in both airand O2-saturated solution, accompanied by formation of 1a as the main reaction product. At longer irradiation times consumption of 1a is observed accompanied by an increase in the amount of 4-methoxybenzaldehyde. In O2saturated solution, in line with the greater efficiency of the TPP+ regeneration process, consumption of 1a occurs significantly faster than in air, and after 10 min of irradiation a decrease in the amount of 4-methoxybenzaldehyde is observed, accompanied by the formation of 4-methoxybenzoic acid. Comparison between entries 2 and 3 shows that both product distribution and substrate consumption are not influenced to a significant extent by the presence of the cosensitizer BP. In the presence of pyridine, formation of ether 1a is strongly depressed as compared to the experiment carried out in the absence of base (compare entries 2 and 4), while a significantly higher amount of substrate 1 is recovered. By increasing irradiation time (entries 7 and 10), an increase in substrate consumption is observed accompanied by an increase in the amount of 4-methoxybenzaldehyde. By increasing pyridine concentration (from 5 × 10-4 to 2.5 × 10-3 M, entries 10-12) the amount of recovered substrate increases while the amount of 4-methoxybenzaldehyde and of ether 1a decreases. Since it is known that sensitizer regeneration requires the presence of H+,8 it may be suggested that at relatively high concentrations, pyridine, due to its basic character, prevents sensitizer regeneration, resulting in a lower substrate conversion. An analogous behavior is observed after addition of 1,2epoxybutane. However, to observe a quantitatively similar effect on substrate consumption and product formation a concentration of 1,2-epoxybutane 200 times higher than that of pyridine is needed. The results of the TPPBF4-photosensitized reaction of bis(4-methoxybenzyl) ether (1a) in air- or O2-saturated CH2Cl2 solution at different irradiation times are collected in Table 2. Under all conditions, consumption of 1a is observed, accompanied by the formation of 4-methoxybenzyl alcohol (1) and 4-methoxybenzaldehyde as main reaction products. At longer irradiation times an increase in the amount of 4-methoxybenzaldehyde is observed while the (8) Jacobi, D.; Abraham, W.; Pischel, U.; Grubert, L.; Stosser, R.; Schnabel, W. J. Chem. Soc., Perkin Trans. 2 1999, 1695-1702.
J. Org. Chem, Vol. 69, No. 25, 2004 8875
Branchi et al. TABLE 1. Product Distributions Observed after TPPBF4-Photosensitized Reaction of 4-Methoxybenzyl Alcohol (1) in CH2Cl2 Solution at Different Irradiation Times, under a Variety of Conditionsa yield (%) entry
irradiation time (min)
air saturated 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
2 5 5 5 5 15 15 15 30 30 30 30 30 30 60
conditionsb
10-2
[BP] ) 5 × M [pyr] ) 5 × 10-4 M [1,2-eb] ) 0.1 M [pyr] ) 5 × 10-4 M [1,2-eb] ) 0.1 M [pyr] ) 5 × 10-4 M [pyr] ) 1 × 10-3 M [pyr] ) 2.5 × 10-3 M [1,2-eb] ) 5 × 10-2 M [1,2-eb] ) 0.1 M
1
AnCHOc
1a
1b
40 27 24 72 79 18 59 60 15 33 58 69 39 47 5
13 19 29 26 22 35 37 38 52 61 41 31 50 52 89
46 52 45 2 1 46 4 2 31 6 1
1 2 2 1 2
11 1 6
yield (%) entry
irradiation time (min)
1
AnCHOc
O2 saturated 16 17 18 19 20 21
1 2 5 10 15 30
48 14 12
15 28 48 96 78 54
1a
1b
36 57 38
1 1 2
AnCO2Hc
4 22 46
a [1] ) 5 × 10-3 M; [TPPBF ] ) 5 × 10-4 M; λ b c 4 irr ) 365 nm; T ) 25 °C. BP ) biphenyl; pyr ) pyridine; 1,2-eb ) 1,2-epoxybutane. An ) 4-MeOC6H4.
TABLE 2. Product Distributions Observed after
TABLE 3. Product Distributions Observed after
TPPBF4-Photosensitized Reaction of Bis(4-methoxybenzyl) Ether (1a) in CH2Cl2 Solution at Different Irradiation Timesa
TPPBF4-Photosensitized Reaction of 4-Methoxytoluene (2) and 4-Methoxybenzyl Methyl Ether (3) in CH2Cl2 Solution at Different Irradiation Times
yield (%) conditions
irradiation time (min)
1a
AnCHOb
1
1b
O2 O2 air air air
2 5 5 15 30
72 43 66 37 20
11 44 20 51 71
14 10 13 11 8
3 3 1 1 1
10-3
[1a] ) 2.5 × M; [TPPBF4] ) 5 × T ) 25 °C. b An ) 4-MeOC6H4. a
10-4
M; λirr ) 365 nm;
amount of 1 decreases. In O2-saturated solution, the reaction occurs significantly faster than in air saturated solution. To obtain information on the role of the R-OH group in the TPPBF4-photosensitized reactions of 1, the TPPBF4-photosensitized reactions of 4-methoxytoluene (2) and 4-methoxybenzyl methyl ether (3), substrates structurally related to 1 but lacking the presence of the R-OH group, were also studied. The results of the TPPBF4photosensitized reactions of 2 and 3 in air- or O2saturated CH2Cl2 solution at different irradiation times are collected in Table 3. After 30 min of irradiation the TPPBF4-photosensitized reaction of 2 leads to the formation of 4-methoxybenzaldehyde as the exclusive product. By increasing irradiation time an increase in the amount of 4-methoxybenzaldehyde is observed, accompanied by the formation of a small amount of 4-methoxybenzyl alcohol (1). In the presence of pyridine a significant increase in the amounts of both 4-methoxybenzaldehyde and 1 is observed. 8876 J. Org. Chem., Vol. 69, No. 25, 2004
yield (%) irrad time recovered substrate conditions (min) substrate AnCHOb 1 AnCO2Meb 2 2 2 3 3
air air air O2 O2
30 60 30c 1 2
96 90 76 94 78
4 9 19 3 13
1 5 1 1
2 8
a [2] ) 5 × 10-3 M; [TPPBF ] ) 5 × 10-4 M; λ 4 irr ) 365 nm; T ) 25 °C. b An ) 4-MeOC6H4. c In the presence of 5 × 10-4 M pyridine.
The TPPBF4-photosensitized reaction of 3 leads instead to the formation of comparable amounts of 4-methoxybenzaldehyde and methyl 4-methoxybenzoate as main reaction products. By increasing irradiation time an increase in the amount of both products is observed. To obtain information on the role of the aromatic ring structure on the TPPBF4-photosensitized reactions of benzyl alcohols, the reactions of 2-methoxybenzyl alcohol (4), 2,4-dimethoxybenzyl alcohol (5), 2,5-dimethoxybenzyl alcohol (6), 3,4-dimethoxybenzyl alcohol (7), and 2,4,5trimethoxybenzyl alcohol (8) were also studied. The results of the TPPBF4-photosensitized reactions of alcohols 4-8 in O2-saturated CH2Cl2 solution are collected in Table 4 where, as a matter of comparison, also the corresponding data obtained for 1 are included. The results collected in Table 4 show that in the TPPBF4-photosensitized reaction of ring-methoxylated benzyl alcohols 1 and 4-8 the product amounts and distributions are strongly influenced by the number and
Oxidation of Ring-Methoxylated Benzyl Alcohols TABLE 4. Product Distributions Observed after TPPBF4-Photosensitized Reaction of Ring-Methoxylated Benzyl Alcohols ArCH2OH (1, 4-8) in O2-Saturated CH2Cl2 Solutiona yield (%) substrate
ArCH2OH
ArCHO
ArCH2OCH2Ar
ArCH2Ar
1 4 5b,c 6 7 8
48 92 88 99 88 92
15 8
