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Synlett 2008(20): 3137-3140  
DOI: 10.1055/s-0028-1087272
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

An Improved Procedure for the Photoacylation of 1,4-Naphthoquinone with Aliphatic Aldehydes

Ferdinand Friedrichsa, Brian Murphya, Delphine Nayrata, Torsten Ahnera, Mario Funkea, Michael Ryana, Johann Lexb, Jochen Mattayc, Michael Oelgemöller*a,1
a School of Chemical Sciences and NCSR, Dublin City University, Glasnevin, Dublin 14, Ireland
Fax: +353(1)7005503; e-Mail: michael.oelgemoeller@dcu.ie;
b Institut für Organische Chemie, Universität zu Köln, Greinstrasse 4, 50939 Köln, Germany
c Organische Chemie I, Fakultät für Chemie, Universität Bielefeld, Postfach 100131, 33501 Bielefeld, Germany
Further Information

Publication History

Received 2 September 2008
Publication Date:
26 November 2008 (online)

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Abstract

Irradiation of 1,4-naphthoquinone at 300±25 nm in benzene and in the presence of aliphatic aldehydes readily yields acylated hydroquinones in good to high yields. The developed protocol represents a significant improvement over the original procedure using medium-pressure mercury lamps. Subsequent oxidation gives the corresponding acylated quinones.

Key words

acylations - photochemistry - quinones - aldehydes

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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

16

Lamp data provided by Luzchem Research Inc., 5509 Canotek Road, Unit 12, Ottawa, Ontario K1J 9J9, Canada (http://www.luzchem.com).

18

General Procedure for Irradiation
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 (λmax = 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): δ = 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, COCH2CH 2), 2.97 (t, 2 H, J = 7.5 Hz, COCH 2), 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): δ = 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): ν = 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.

19

Crystal Data for 3b
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; β = 96.176 (1)˚; V = 2084.23 (12) ų; Z = 8; d calc  = 1.378
g/cm³; R = 0.0714, R W = 0.110 for 3198 reflections having F > 2σ(F).
Crystal Data for 3g
Brownish-yellow prisms (from benzene), mp 139-142 ˚C, C17H20O3, FW = 272.33 g/mol, orthorhombic, space group Pccn; a = 24.9503 (11), b = 12.8054 (4), c = 8.9576 (3) Å; V = 2861.94 (18) ų; Z = 8; d calc  = 1.378 g/cm³; R = 0.0721, R W = 0.1057 for 2099 reflections having F > 2σ(F).
Further crystallographic data have been deposited at the Cambridge Crystallographic Data Centre (CCDC-692479 and CCDC-692480). These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif.

21

General Procedure for Oxidation
Acylated photoproduct (1.5 mmol) was dissolved in anhyd Et2O (50 mL). Anhyd Na2SO4 (3.0 g, 21 mmol) was added, followed by freshly prepared Ag2O (575 mg, 2.5 mmol) in small portions.²² The suspension was stirred overnight in the dark at r.t. (TLC control: silica gel, EtOAc-n-hexane mixtures), filtered over a pad of Celite, and concentrated to dryness. The crude product was recrystallized from cold Et2O. Filtration and drying in vacuum gave the desired acylated naphthoquinones 4.
Selected Physical and Spectral Data for 2-Undecanoyl-1,4-naphthoquinone (4l)
Yellow solid, mp 62-64 ˚C. ¹H NMR (400 MHz, CDCl3): δ = 0.88 (t, 3 H, J = 6.8 Hz, CH3), 1.20-1.40 (br m, 16 H, 8 × CH2), 1.68 (dq, 2 H, J = 7.2 Hz, COCH2CH 2), 2.93 (t, 2 H, J = 7.2 Hz, COCH 2), 7.08 (s, 1 H, Hquin.), 7.81 (m, 2 H, ArH), 8.10 (m, 2 H, ArH). ¹³C NMR (100 MHz, CDCl3): δ = 14.3, 22.8, 23.7, 29.2, 29.4, 29.5, 29.6, 29.7, 29.8, 32.1, 43.7, 126.5, 127.0, 131.8, 131.9, 134.5, 134.7, 136.7, 146.2, 183.5, 185.2, 201.2. IR (KBr): ν = 2951, 2852, 1696, 1672, 1589, 1495, 1452, 1296, 1251, 1224, 1050, 878, 824, 714 cm-¹. HRMS (EI+): m/z calcd for 340.20385; found: 340.20326.