Solvent was then removed under a reduced pressure to give a
Dicyclopropylmethyl 2,4-dinitrobenzenesulfenate 9b. Crys-
1
◦
clear oil (4.5 g, 0.0401 mol, 89%). 1H NMR 300 MHz d 0.24 (m,
tallised from CH2Cl2 (mp 113–116 C). H NMR d (CDCl3)
0.50 (m, 4H), 0.66 (m, 4H), 1.22 (m, 2H), 4.08 (t, J = 8.6), 7.9
(d, J = 10 Hz, 1H), 8.5 (1H, dd, J = 2.2, 10 Hz), 8.8 (d, J =
2.2 Hz).
4H), 0.44 (m, 4H), 0.96 (m, 2H), 1.95 (bs, 1H), 2.38 (t, 1H); 13
C
NMR d (CDCl3) 79.8, 16.8, 2.0.
Cyclopropylmethyl picrate 8a. A solution of cyclopropyl-
methanol 8 (0.07 g, 97 mmol) in CH2Cl2 (20 ml) and triethy-
lamine (0.8 ml) was treated with 2,4,6-trinitrofluorobenzene
(0.29 g, 0.76 mmol). After stirring for 3 h the solution was
washed with water (3 × 20 ml), HCl (0.1 M, 2 × 20 ml) and
then 5% aqueous NaHCO3 (1 × 20 ml), dried (MgSO4) and
evaporated under a reduced pressure to afford a yellow solid.
Crystallised f◦rom methanol gave 8a (190 mg) as yellow slabs
(mp 143–145 C). 1H NMR d (CDCl3) 9.15 (s, 2H), 4.12 (d, J =
7.3, 2H), 1.3 (m, 1H), 0.66 (m, 2H), 0.34 (m, 2H); 13C NMR d
(CDCl3) 149.7, 145.1, 140.2, 123.1, 84.4, 10.5, 3.7.
X-ray crystallography
Intensity data were collected with a Bruker SMART Apex CCD
detector using MoKa radiation (graphite crystal monochroma-
tor k = 0.71073). The temperature was maintained at 130.0(1)
using an Oxford Cryostream cooling device. Data were reduced
using the program SAINT.24 The structure was solved by direct
methods and difference fourier synthesis using the SHELX25
suite of programs as implemented with the WINGX26 software.†
References
Cyclopropylmethyl
p-nitrophenoxide
8f. Cyclopropyl
methanol 8 (107 mg, 1.48 × 10−3 mol) was added to a slurry
1 J. M. White and C. I. Clark, Topics in Stereochemistry, ed. S. E. Den-
mark, John Wiley and Sons, New York, 1999, vol. 22, ch. 3, p. 137.
2 P. Deslongchamps, Stereoelectronic Effects in Organic Chemistry,
Organic Chemistry Series Volume 1, ed. J. E. Baldwin, Pergamon
Press, Oxford, 1983.
3 (a) R. S. Mulliken, J. Chem. Phys., 1939, 7, 339; (b) A. N. Egorochkin,
Russ. Chem. Rev., 1984, 53, 445; (c) R. Gleiter, Pure Appl. Chem.,
1987, 59, 1585; (d) N. Muller and R. S. Mulliken, J. Am. Chem. Soc.,
1958, 80, 3489.
4 D. D. Davis, J. Organomet. Chem., 1981, 206, 21; M. A. Cook, C.
Eaborn and D. R. M. Walton, J. Organomet. Chem., 1970, 24, 293.
5 W. Hanstein, H. J. Berwin, T. G. Traylor and T. G., J. Am. Chem.
Soc., 1970, 92, 829.
of NaH (90 mg, 3.8 × 10−3 mol) in anhydrous THF (50 ml) at
0
◦C. The mixture was stirred for 1 h under N2 then treated
with p-fluoronitrobenzene (0.239 g, 1.69 × 10−3 mol) and
stirred overnight. The mixture was diluted with water (50 ml),
extracted into ether (3 × 50 ml) and the combined ether extracts
washed with water (3 × 100 ml). The organic phase was dried
(MgSO4), filtered and the solvent removed under a reduced
pressure to yield the ether 8f as an oil which slowly crystallised
◦
1
at low temperature (mp 9–10 C) (150 mg, 57%). H NMR d
(CDCl3) 0.35 (m, 2H), 0.61 (m, 2H), 0.80 (m, 1H), 3.85 (d, J =
6.8 Hz, 2H), 6.9 (d, J = 7.6 Hz, 2H), 8.1 (d, J = 7.6 Hz, 2H);
13C NMR d (CDCl3) 163.9, 141.1, 125.6, 114.3, 73.3, 9.8, 3.0.
6 W. Adcock, D. P. Cox and W. Kitching, J. Organomet. Chem., 1977,
133, 393.
7 I. V. Alabugin, J. Org. Chem., 2000, 65, 3910.
General synthesis of ester derivatives. Cyclopropylmethanol
8 (103 mg, 1.43 × 10−3 mol) and p-nitrobenzoyl chloride (333 mg,
1.79 × 10−3 mol) were stirred together in pyridine (1 ml) under
N2 for four hours. Water (1–2 drops) was added to quench the
reaction, the product was extracted into ether (3 × 50 ml) and
the combined organic extracts washed with sat. CuSO4 solution
(2 × 50 ml), water (50 ml) and NaHCO3 (50 ml). The organic
phase was dried (MgSO4) and solvent removed under a reduced
pressure to yield cyclopropylmethyl p-nitrobenzoate 8e (250 mg,
1.1 × 10−3, 79%). The product was crystallised from hot ether
(mp 52–55 ◦C, lit23 56–57 ◦C). 1H NMR d (CDCl3) 0.39 (m, 2H,),
0.65 (m, 2H), 1.22 (m, 1H,), 4.20 (d, 2H, J = 7.3 Hz), 8.24 (d,
2H, J = 8.7 Hz), 8.29 (d, 2H, J = 8.7 Hz); 13C NMR d (CDCl3)
164.7, 150.4, 135.8, 130.6, 123.4, 70.7, 9.74, 3.36.
8 A. J. Briggs, R. Glenn, P. G. Jones, A. J. Kirby and P. Ramaswamy,
J. Am. Chem. Soc., 1984, 106, 6200.
9 R. D. Amos, N. C. Handy, P. G. Jones, A. J. Kirby, J. K. Parker, J. M.
Percy and M. D. Su, J. Chem. Soc., Perkin Trans. 2, 1992, 4, 549.
10 A. J. Green, J. Giordano and J. M. White, Aust. J. Chem., 2000, 53,
285.
11 M. Spiniello and J. M. White, Org. Biomol. Chem., 2003, 1, 3094.
12 (a) A. J. Kirby, The Anomeric Effect and Related Stereoelectronic
Effects at Oxygen, ed. K. Hafner, J.-M. Lehn, C. W. Rees, P. van
Rague Schleyer, B. M. Trost and R. Zahradnik, Springer-Verlag,
Berlin, 1983.
13 J. B. Lambert, Tetrahedron, 1990, 46, 2677.
14 R. Gleiter, G. Jahne, M. Oda and M. Iyoda, J. Org. Chem., 1985, 50,
678.
15 E. Uggerud, D. Arad, Y. Apeloig and H. Schwarz, J. Chem. Soc.,
Chem. Commun., 1989, 1015.
16 T. G. Traylor, W. Hanstein, H. J. Berwin, N. A. Clinton and R. S.
Brown, J. Am. Chem. Soc., 1971, 93, 5715.
Cyclopropylmeth◦yl 3,5-dinitrobenzoate 8d. Crystallised from
ether (mp 103–105 C). 1H NMR d (XDXk3) 0.42 (2H), 0.69 (m,
2H), 1.32 (m, 1H), 4.28 (d, J = 7.6), 9.19 (d, J = 1.9, 2H), 9.23
(t, J = 1.9, 1H); 13C NMR d (CDCl3) 162.6, 148.6, 134.2, 129.5,
122.2, 71.9, 9.7, 3.6.
17 A. Streitwieser Jr. and S. Alexandratos, J. Am. Chem. Soc., 1978, 100,
1979.
18 A. de Meijere, Angew. Chem., Int. Ed. Engl., 1979, 18, 809.
19 H. C. Brown and E. N. Peters, J. Am. Chem. Soc., 1973, 95, 2400.
20 Y. Apeloig and D. Arad, J. Am. Chem. Soc., 1985, 107, 5285.
21 F. H. Allen, O. Kennard, R. Taylor and R., Acc. Chem. Res., 1983,
16, 146.
22 H. Hart and O. E. Curtis Jr., J. Am. Chem. Soc., 1956, 78, 112.
23 W. D. Clossen and G. T. Kwiatowski, Tetrahedron, 1965, 21, 2779.
24 Siemens 1999, SMART, SAINT, SADABS, Siemens Analytical X-ray
Instruments Inc., Madison, Wisconsin, USA.
25 SHELX97 [includes SHELXS97, SHELXL97]–Programs for solu-
tion of crystal structures (release 97-2), G. M. Sheldrick, Institut fur
Anorganische Chemie der Universitat, Tammanstrasse 4, D-3400
Gottingen, Germany, 1998.
Cyclopropylmethyl 2,4-dinitrobenzenesulfenate 8c. Crys-
◦
1
tallised from methanol (mp 90–91 C). H NMR d (CDCl3)
0.39 (m, 2H), 0.68 (m, 2H), 1.29 (m, 1H), 3.8 (d, J = 7.3, 2H),
8.0 (d, J = 9.1, 1H), 8.5 (dd, J = 2.2, 9.1, 1H), 9.13 (d, J =
2.2, 1H). 13C NMR d (CDCl3) 154.8, 144.3, 139.2, 127.7, 123.4,
121.1, 82.8, 11.2, 3.8.
Cyclopropylmethyl 2,4-dinitrobenzoate 8b. Crystallised from
pentane (mp 49–51 ◦C). 1H NMR 300 MHz d 0.32 (m, 2H), 0.67
(m, 2H), 1.35 (m, 1H), 4.16 (d, J = 7.3, 1H), 7.86 (d, J = 8.3,
1H), 8.52 (dd, J = 8.4, 2.2 Hz, 1H), 8.78 (d, J = 2.2, 1H). 13C
NMR d (CDCl3) 163.7, 148.8, 133.0, 131.2, 127.4, 119.4, 72.2,
9.3, 3.3.
26 L. J. Farrugia, J. Appl. Crystallogr., 1999, 32, 837.
Dicyclopropylmethyl p-nitrobenzoate 9d. Crystallised from
pentane (mp 65–68 ◦C). 1H NMR d (CDCl3) 0.39 (m, 4H), 0.56
(m, 4H), 1.17 (m, 2H), 4.19 (t, J = 6.8Hz) 8.24 (d, J = 7.4,
2H), 8.29 (d, J = 7.4); 13C NMR, d (CDCl3) 164.4, 150.3, 136.3,
130.7, 123.4, 84.0, 14.7, 2.8, 2.95.
† CCDC reference numbers 265209–265216. See http://www.rsc.org/
suppdata/ob/b5/b503124a/ for crystallographic data in CIF or other
electronic format.
1 7 8 0
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 1 7 7 6 – 1 7 8 0