LETTER
Efficient Photoacylation of 1,4-Naphthoquinone
3139
(11) Sharma, P. K.; Khanna, R. N. Monatsh. Chem. 1985, 116,
353.
Table 2 Isolated Product Yields for Photoacylations and Oxidations
(12) (a) For a recent review on the photoacylation of quinones,
see: Oelgemöller, M.; Mattay, J. In CRC Handbook of
Organic Photochemistry and Photobiology, 2nd ed.;
Horspool, W. M.; Lenci, F., Eds.; CRC: Boca Raton, 2004,
Chap. 88, 1–45. (b) For a general review on the
photochemistry of quinones, see: Maruyama, K.; Osuka, A.
In The Chemistry of Quinonoid Compounds, Vol. 2; Patai,
S.; Rappoport, Z., Eds.; John Wiley & Sons: New York,
1988, Chap. 13, 759–878.
(13) (a) Waske, P. A.; Mattay, J.; Oelgemöller, M. Tetrahedron
Lett. 2006, 47, 1329. (b) Oelgemöller, M.; Schiel, C.;
Fröhlich, R.; Mattay, J. Eur. J. Org. Chem. 2002, 2465.
(c) Schiel, C.; Oelgemöller, M.; Mattay, J. Synthesis 2001,
1275. (d) Schiel, C.; Oelgemöller, M.; Ortner, J.; Mattay, J.
Green Chem. 2001, 3, 224. (e) Schiel, C.; Oelgemöller, M.;
Mattay, J. J. Inf. Rec. 1998, 24, 257.
(14) (a) Kraus, G. A.; Kirihara, M. J. Org. Chem. 1992, 57, 3256.
(b) Kraus, G. A.; Liu, P. Tetrahedron Lett. 1994, 35, 7723.
(15) Maruyama, K.; Miyagi, Y. Bull. Chem. Soc. Jpn. 1974, 47,
1303.
(16) Lamp data provided by Luzchem Research Inc., 5509
Canotek Road, Unit 12, Ottawa, Ontario K1J 9J9, Canada
(http://www.luzchem.com).
Entry
R
Photoacylation
Oxidation
Time (h) 3 (yield, %)
4 (yield, %)
1
2
Me
23
23
22
30
28
28
27
20
27
27
28
28
3a (75)
3b (73)
3c (58)
3d (56)a
3e (80)
3f (77)
3g (75)
3h (68)
3i (69)
3j (58)
3k (61)
3l (69)
4a (58)
4b (92)
4c (88)
4d (72)
4e (92)
4f (75)
4g (75)
4h (96)
4i (89)
4j (92)
4k (93)
4l (95)
Et
3
Pr
4
i-Pr
5
Bu
6
C5H11
C6H13
C7H15
C8H17
C9H19
C10H21
C11H23
7
8
9
10
11
12
(17) Singh, I.; Ogata, R. T.; Moore, R. E.; Chang, C. W.; Scheuer,
P. J. Tetrahedron 1968, 24, 6053.
(18) General Procedure for Irradiation
a After column chromatography (incomplete reaction).
In a typical photochemical experiment, a solution of
naphthoquinone (1 mmol) and aldehydes (5 mmol) in anhyd
benzene (50 mL) was degassed with argon and irradiated in
a Pyrex vessel for 22–30 h using a Rayonet Photochemical
reactor (RPR-200; Southern New England Ultraviolet
Company) equipped with RPR-3000 Å lamps
(lmax = 300 25 nm). The large-scale reaction was performed
with 20 mmol of 1 and 140 mmol of 2b in 100 mL of
benzene instead. The reaction was continued until TLC
analysis (silica gel, EtOAc–n-hexane mixtures) indicated
complete consumption of the quinone. The solution was
evaporated to a smaller volume of about 10 mL. On standing
at 0 °C (fridge) the photoproducts readily precipitated
(several crops). Filtration, washing with cold benzene,
followed by cold n-hexane, and drying in vacuum gave the
desired products 3.
Selected Physical and Spectral Data for 1-(1,4-
Dihydroxynaphthalen-2-yl)-dodecan-1-one (3l)
Yellow solid, mp 100–102 °C. 1H NMR (400 MHz, CDCl3):
d = 0.88 (t, 3 H, J = 6.8 Hz, CH3), 1.21–1.46 (br m, 16 H,
8 × CH2), 1.78 (dq, 2 H, J = 7.5, 7.2 Hz, COCH2CH2), 2.97
(t, 2 H, J = 7.5 Hz, COCH2), 4.96 (br s, 1 H, 4-OH), 7.03 (s,
1 H, ArH), 7.58 (ddd, 1 H, J = 8.4, 7.2, 1.4 Hz, ArH), 7.68
(ddd, 1 H, J = 8.4, 7.2, 1.4 Hz, ArH), 8.10 (dd, 1 H, J = 8.4,
1.2 Hz, ArH), 8.46 (dd, 1 H, J = 8.4, 1.2 Hz, ArH), 13.79 (s,
1 H, 1-OH). 13C NMR (100 MHz, CDCl3): d = 14.3, 22.8,
24.7, 29.4, 29.5, 29.6, 29.7, 29.8, 29.9, 32.5, 39.0, 105.6,
111.8, 121.6, 124.8, 126.3, 126.7, 129.4, 129.8, 143.0,
157.6, 206.2. MS (EI): m/z = 342 [M+], 324, 215, 202, 197,
187, 173, 131, 77, 55, 43. IR (KBr): n = 3340, 2950-2850,
1640, 1590, 1460, 1400, 1290, 1190, 1140, 1080, 1040, 880,
820, 770 cm–1. HRMS (EI+): m/z calcd for 342.21949; found:
342.21883.
References and Notes
(1) New address from 2009: School of Pharmacy and Molecular
Sciences, James Cook University, Townsville, Queensland
4811, Australia. E-mail: michael.oelgemoeller@jcu.edu.au
(2) (a) Thomson, R. H. Naturally Occurring Quinones IV;
Blackie: Glasgow, 1996. (b) Thomson, R. H. Naturally
Occurring Quinones III, Recent Advances; Chapman &
Hall: London, 1987. (c) Bérdy, J.; Aszalos, A.; Bostian, N.;
McNitt, K. L. CRC Handbook of Antibiotic Compounds.
Quinone and Similar Antibiotics, Vol. 3; CRC: Boca Raton,
1980. (d) The Chemistry of the Quinonoid Compounds;
Patai, S., Ed.; John Wiley & Sons: New York, 1974.
(3) (a) Hase, J.; Nishimura, T. J. Pharm. Soc. Jpn. 1955, 75,
203. (b) Hase, J.; Nishimura, T. J. Pharm. Soc. Jpn. 1955,
75, 207.
(4) (a) Suganuma, H. J. Synth. Org. Chem. Jpn. 2001, 59, 23.
(b) Koura, Y.; Kinoshita, S.; Takasuka, K.; Koura, S.; Osaki,
N.; Matsumoto, S.; Miyoshi, H. J. Pesticide Sci. 1998, 23,
18.
(5) (a) Papapgeorgiou, V. P.; Assimopoulou, A. N.;
Couladouros, E. A.; Hepworth, D.; Nicolaou, K. C. Angew.
Chem. Int. Ed. 1999, 38, 270; Angew. Chem. 1999, 111,
280. (b) Couladouros, E. A.; Strongilos, A. T. Eur. J. Org.
Chem. 2002, 3341.
(6) (a) For pyrano-[2,3-c]-naphthoquinone antibiotics, see:
Brimble, M. A.; Nairn, M. R.; Prabaharan, H. Tetrahedron
2000, 56, 1937. (b) For 1,4-benzodiazepines, see: Kraus,
G. A.; Maeda, H. Tetrahedron Lett. 1994, 35, 9189. (c) For
lapachones, see: Maruyama, K.; Naruta, Y. Chem. Lett.
1977, 847.
(7) Kurosawa, E.; Quinones, I. Bull. Chem. Soc. Jpn. 1961, 34,
300.
(19) Crystal Data for 3b
(8) Yadav, J. S.; Subba Reddy, B. V.; Swamy, T.;
Raghavender Rao, K. Tetrahedron Lett. 2004, 45, 6037.
(9) Rathwell, K.; Brimble, M. A. Synthesis 2007, 643.
(10) Boyer, J. L.; Krum, J. E.; Myers, M. C.; Fazal, A. N.; Wigal,
C. T. J. Org. Chem. 2000, 65, 4712.
Brownish-yellow prisms (from benzene), mp 164–166 °C,
C13H12O3, FW = 216.23 g/mol, monoclinic, space group
P21/c; a = 11.1180 (3), b = 8.8795 (3), c = 21.2353 (8) Å;
b = 96.176 (1)°; V = 2084.23 (12) Å3; Z = 8; dcalc = 1.378
g/cm3; R = 0.0714, RW = 0.110 for 3198 reflections having
F > 2s(F).
Synlett 2008, No. 20, 3137–3140 © Thieme Stuttgart · New York