PAPER
Synthesis of Anhydrides and Esters
3495
Phenyl Levulinate (3jh)
(4) Organic carbonates, for example, find employment as fuel
additives, lubricating oils, herbicides, pesticides, plastics
and solvents, and for medicinal and biological applications.
(5) Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic
Synthesis, 3rd ed.; Wiley: New York, 1999, 518–525.
(6) Ref. 5, p 281.
(7) Takeda, K.; Akiyama, A.; Nakamura, H.; Takizawa, S.;
Mizuno, Y.; Takayanagi, H.; Harigaya, Y. Synthesis 1994,
1063.
Mp 31–32 °C (Lit.47 32 °C).
1H NMR (400 MHz, CDCl3): d = 2.22 (s, 3 H), 2.79–2.89 (m, 4 H),
7.05–7.16 (m, 2 H), 7.18–7.26 (m, 1 H), 7.32–7.41 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 28.13 (CH2), 29.84 (CH3), 37.90
(CH2), 121.48 (2 × CH), 125.79 (CH), 129.37 (2 × CH), 150.65 (C),
171.42 (C), 206.37 (C).
MS (EI): m/z (%) = 192 (1) [M+], 99 (100), 94 (70), 71 (16), 65 (11),
(8) Gooßen, L.; Döhring, A. Adv. Synth. Catal. 2003, 345, 943.
(9) Bartoli, G.; Bosco, M.; Carlone, A.; Dalpozzo, R.; Locatelli,
M.; Melchiorre, P.; Sambri, L. J. Org. Chem. 2006, 71, 9580.
(10) (a) Pope, B. M.; Sheu, S.-J.; Stanley, R. L.; Tarbell, D. S.;
Yamamoto, Y. J. Org. Chem. 1978, 43, 2410. (b) Dean, C.
S.; Tarbell, D. S.; Friederang, A. W. J. Org. Chem. 1970, 35,
3393.
(11) Gooßen, L.; Döhring, A. Synlett 2004, 263.
(12) Bartoli, G.; Bosco, M.; Locatelli, M.; Marcantoni, E.;
Melchiorre, P.; Sambri, L. Org. Lett. 2005, 7, 427.
(13) By comparison, Gooßen obtained methyl 3-phenylpropan-
oate(3ac) in 93% yield after 16 hours at room temperature by
mixing acid 1a, Moc2O (2c) and Mg(ClO4)2 in nitromethane
(4 mL) in the ratio 1:1.3:0.01, respectively.
55 (10).
Anal. Calcd for C11H12O3: C, 68.75; H, 6.25. Found: C, 68.70; H,
6.25.
4-Chlorophenyl 3-Hexenoate (3li)
Oil.
1H NMR (400 MHz, CDCl3): d = 1.02 (t, J = 7.46 Hz, 3 H), 2.03–
2.15 (m, 2 H), 3.26 (app dq, Jd = 6.6 Hz, Jq = 1.1 Hz, 2 H), 5.53–
5.77 (m, 2 H), 7.00–7.06 and 7.29–7.35 (A2B2 system, 2 H + 2 H).
13C NMR (100 MHz, CDCl3): d = 13.38 (CH3), 25.50 (CH2), 37.95
(CH2), 119.60 (CH), 122.87 (2 × CH), 129.38 (2 × CH), 131.08 (C),
137.24 (CH), 149.15 (C), 170.33 (C).
MS (EI): m/z (%) = 224/226 (2, isomer ratio 3:1) [M+], 128/130 (52,
isomer ratio 3:1), 96 (100), 81 (33), 69 (64).
(14) The water molecules associated with the hydrated form of a
Lewis acid catalyst allow the formation of a loose transition
state, see: Chakraborti, A. K.; Sharma, L.; Gulhane, R.;
Shivani Tetrahedron 2003, 59, 7661.
Anal. Calcd for C12H13ClO2: C, 64.11; H, 5.79; Cl, 15.85. Found: C,
64.15; H, 5.80; Cl, 15.85.
(15) In a blank run, ethanol and dicarbonate 2a were allowed to
react in the presence of 10 mol% of magnesium chloride at
room temperature and, after 48 hours, no appreciable
amount of carbonate was detected.
(16) For recent literature, see among others: (a) Pasha, M. A.;
Rizwana, S. Indian J. Chem., Sect. B: Org. Chem. Incl. Med.
Chem. 2005, 44, 420. (b) Jabbar, S.; Banerjee, S. Asian J.
Chem. 2002, 14, 1655.
(17) Bartoli, G.; Boeglin, J.; Bosco, M.; Locatelli, M.;
Massaccesi, M.; Melchiorre, P.; Sambri, L. Adv. Synth.
Catal. 2005, 347, 33; and references cited therein.
(18) (a) Staab, H. A. Angew. Chem., Int. Ed. Engl. 1962, 1, 351.
(b) Neises, B.; Steglich, W. Angew. Chem., Int. Ed. Engl.
1978, 17, 522. (c) Mitsonobu, O. Synthesis 1981, 1.
(19) In contrast to magnesium perchlorate, which has a high
activity for esterification (see ref. 9), magnesium chloride is
unable to catalyze esterification between acid 1a and alcohol
4a in reaction times comparable with those reported in
Table 2.
(20) Biermann, U.; Metzger, J. O. J. Am. Chem. Soc. 2004, 126,
10319.
(21) Armesto, N.; Ferrero, M.; Fernández, S.; Gotor, V. J. Org.
Chem. 2003, 68, 5784.
(22) Dhimitruka, I.; SantaLucia, J. Jr. Org. Lett. 2006, 8, 47.
(23) Park, Y. D.; Kim, J. J.; Kim, H. K.; Cho, S. D.; Kang, Y. J.;
Park, K. H.; Lee, S. G.; Yoon, Y. J. Synth. Commun. 2005,
35, 371.
(24) Köster, R.; Sporzynski, A.; Schüßler, W.; Bläser, D.; Boese,
R. Chem. Ber. 1994, 127, 1191.
Acknowledgment
This work was carried out in the framework of the National Project
‘Stereoselezione in Sintesi Organica. Metodologie e Applicazioni’
supported by MIUR, Rome, by the University of Bologna, in the
framework of ‘Progetto di Finanziamento Pluriennale, Ateneo di
Bologna’, and by National Project FIRB ‘Progettazione, prepara-
zione e valutazione biologica e farmacologica di nuove molecole
organiche quali potenziali farmaci’.
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Synthesis 2007, No. 22, 3489–3496 © Thieme Stuttgart · New York