204 JOURNAL OF CHEMICAL RESEARCH 2007
Table 3 Comparison of protocols for the acylation of t-butanol
Entry
Reagent/catalyst
Acylating agent
Time/min
Temp/°C
Yield/%
References
1
2
3
4
5
6
7
8
SmI2
PhCOCl
6
68
68
25
96
95
67
a
a
SmI2
PhCH2COCl
PhCOCl
3
Zn
Al2O3
ZnO
ZrOCl2
Pyridine
t-BuOLi
90
6
PhCOCl
No reaction
120
7
PhCOCl
40
45
8
PhCOCl
No report
900
900
9
PhCH2COCl
PhCH2COCl
Reflux
RT
45
47
10
11
aPresent work.
We thank the National Natural Science Foundation of China
(No. 20472048 and 20572068) for support of this work.
Experimental
IR spectra were recorded with a Perkin-Elmer 580 spectrometer.
1H NMR spectra were recorded on a Bruker AM-300 spectrometer
in CDCl3 with TMS as an internal standard. Tetrahydrofuran was
freshly distilled from sodium/benzophenone ketyl prior to its use.
Received 6 February 2007; accepted 31 March 2007
Paper 07/4459
doi: 10.3184/030823407X207068
General experimental procedure: To
a mixture of t-butanol
References
(1.0 mmol) and samarium diiodide (0.75 mmol, freshly prepared)
in THF (10 ml) was added the acid chloride (1.0 mmol) with stirring
at 68°C under a nitrogen atmosphere. The progress of the reaction
was monitored by TLC. After completion of the reaction (Table 2),
the resulting mixture was quenched with saturated sodium bicarbonate
solution (20 ml) and extracted with dichloromethane (2 × 10 ml).
The combined extracts were dried with anhydrous magnium sulfate,
and concentrated under reduced pressure. The residue was purified
by column chromatography on silica gel eluting with petroleum
ether/ethyl acetate (100:1) to afford the products. All of the products
are known and were identified by their IR and 1H NMR spectra
(for AA'XX' systems J* = J23 + J25).
1
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2
3
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Synlett., 2002, 826.
1. t-butyl benzoate: Oil (lit.12); νmax (KBr)/cm-1 2977, 2927, 1718,
1594, 1488, 1458, 1368, 1293, 1092; δH (CDCl3/TMS): 8.0 (d,
J = 9.6 Hz, 2H), 7.52–7.38 (m, 3H), 1.58 (s, 9H).
4
5
2. t-butyl 2-chlorobenzoate: Oil (lit.13); νmax (KBr)/cm-1 3063,
2973, 2930, 1725, 1594, 1488, 1369, 1254, 1113; δH (CDCl3/TMS):
7.84 (d, J = 7.5 Hz, 1H), 7.39–7.30(m, 3H), 1.51 (s, 9H).
3. t-butyl 4-chlorobenzoate: Oil (lit.14); νmax (KBr)/cm-1 3061,
2978, 2932, 1713, 1603, 1478, 1451, 1368, 1293, 1115; δH (CDCl3/
TMS): 7.84 (d, J* = 9.0 Hz, 2H), 7.29 (d, J* = 9.0 Hz, 2H), 1.46
(s, 9H).
6
7
8
M.H. Sarvari and H. Aharghi, Tetrahedron, 2005, 61, 10903.
V.K. Yadav and K.G. Babu, J. Org. Chem., 2004, 69, 577.
F. Tamaddon, M.A. Amrollahi and L. Sharafat, Tetrahedron Lett., 2005,
46, 7841.
4. t-butyl 4-methylbenzoate: Oil (lit.14); νmax (KBr)/cm-1 2977,
2927, 1712, 1612, 1457, 1368, 1292, 1109; δH (CDCl3/TMS): 7.88
(d, J* = 8.4 Hz, 2H), 7.20(d, J* = 8.4 Hz,2H), 2.39 (s, 3H), 1.56
(s, 9H).
9
R. Ghosh, S. Maiti and A. Chakraborty, Tetrahedron Lett., 2005, 46, 147.
10 C.R. Hauser, B.E. Hudson, B. Abramovitch and J.C. Shivers, Org.
Synth. Coll. Vol. III; E.C. Horing (ed). John Wiley and Sons, INC:
NY, 1955, 142.
11 G.P. Crowther, E.M. Kaiser, R.A. Woodruff and C.R. Hauser, Org.
Synth. Coll. Vol. VI; W.E. Noland (ed). John Wiley and Sons, INC: NY,
1988, 259.
12 S.W. Wright, D.L. Hageman, A.S. Wright and L.D. McClure, Tetrahedron
Lett., 1997, 38, 7345.
13 S. Ohta, A. Shimabayashi, M. Aono and M. Okamoto, Synthesis,
1982, 833.
5. t-butyl 4-methoxybenzoate: Oil (lit.14); νmax (KBr)/cm-1 2976,
2934, 1708, 1606, 1458, 1368, 1292, 1102; δH (CDCl3/TMS): 7.93
(d, J* = 9.6 Hz, 2H), 6.87(d, J* = 9.6 Hz, 2H), 3.82 (s, 3H), 1.54
(s, 9H).
6. t-butyl cinnamate: Oil (lit.14); νmax (KBr)/cm-1 3061, 3028,
2978, 2931, 1708, 1637, 1578, 1496, 1392, 1283, 1207, 1150;
δH (CDCl3/TMS): 7.59 (d, J = 16.2 Hz, 1H), 7.50–7.33 (m, 5H), 6.37
(d, J = 16.2 Hz, 1H), 1.54 (s, 9H).
7. t-butyl phenylacetate: Oil (lit.15); νmax (KBr)/cm-1 3064, 3031,
2978, 2927, 1734, 1604, 1496, 1455, 1368, 1298, 1142; δH (CDCl3/
TMS): 7.12–7.20 (m, 5H), 3.41 (s, 2H), 1.33 (s, 9H).
14 M.G. Stanton and M.R. Gagne, J. Org. Chem., 1997, 62, 8240.
15 K. Nagasawa, S. Yoshitake, T. Amiya and K. Ito, Synth. Commun., 1990,
20, 2033.
PAPER: 07/4459