Chem. Biodiversity 2016, 13, 1202 – 1220
1219
added giving
19 mmol) in H2O (37.5 ml) was added with stirring over compound was synthesized according to the General Proce-
a period of 30 min. After stirring for further 3 h, the mix- dure for the esterification of acids using 4-methylheptanoic
ture was filtered, acidified with HCl, washed with Et2O, acid (30, 100 mg, 0.694 mmol), 14-methylheptadecan-1-ol
and the org. phase was separated. The aq. phase was (34, 218 mg, 0.810 mmol), abs. CH2Cl2 (7 ml), DMAP
a
homogeneous soln. NaOH (775 mg,
14-Methylheptadecyl 4-Methylheptanoate (5). This
washed twice with Et2O. The combined org. phases were (8 mg, 0.0694 mmol), and EDC (148 mg, 0.771 mmol). Rf
1
dried (MgSO4) and concentrated to give a yellowish crude 0.72 (10:1 pentane/Et2O). Yield: 82% (227 mg). H-NMR
product. Purification was carried out by CC using 3:1 pen- (400 MHz, CDCl3): 0.82 (t, J = 6.9, 6 H); 0.90 (d, J = 6.8, 6
tane/Et2O as solvent mixture. Rf 0.69 (3:1 pentane/Et2O). H); 1.19 – 1.33 (m, 30 H); 1.36 – 1.50 (m, 2 H); 1.60 – 1.69
Yield: 58% (400 mg). 1H-NMR (400 MHz, CDCl3): 0.86 (m, 4 H); 2.30 (dd, J = 9.8, 8.2, 2 H); 4.07 (t, J = 6.7, 2 H).
(t, J = 6.8, 3 H); 0.89 (d, J = 7.0, 3 H); 1.23 – 1.28 (m, 2
13C-NMR (100 MHz, CDCl3): 14.2; 14.4; 19.9 (29); 20.0;
H); 1.32 (q, J = 8.7, 2 H); 1.45 – 1.51 (m, 1 H); 1.63 (dt, 20.1; 25.3; 27.0; 29.0; 29.5; 29.6 (69); 30.0; 31.9; 32.1 (29);
J = 9.1, 8.2, 2 H); 2.3 (t, J = 7.0, 2 H). 13C-NMR
(100 MHz, CDCl3): 14.2; 19.1; 19.9; 31.6; 31.8; 32.0; 38.8;
180.5. EI-MS (70 eV): 145 (43, M+), 127 (15), 112 (29), 84
(61), 71 (53), 57 (58), 43 (100).
32.4; 37.0; 38.9; 39.4; 64.4; 174.2. EI-MS (70 eV): 396 (6,
M+), 339 (6), 325 (9), 297 (4), 253 (4), 209 (5), 145 (100),
127 (24), 109 (26), 97 (30), 83 (35), 69 (32), 57 (42), 43 (73).
Heptadecyl 4-Methylheptanoate (4). This compound
was synthesized according to the General Procedure for
the esterification of acids using 4-methylheptanoic acid
(30, 100 mg, 0.694 mmol), heptadecan-1-ol (31, 207 mg,
0.810 mmol), abs. CH2Cl2 (7 ml), DMAP (8 mg,
0.0694 mmol), and EDC (148 mg, 0.771 mmol). Rf 0.72
(10:1 pentane/Et2O). Yield: 80% (210 mg).1H-NMR
(400 MHz, CDCl3): 0.86 (t, J = 6.8, 6 H); 0.89 (d, J = 7.1,
3 H); 1.21 – 1.41 (m, 32 H); 1.43 – 1.49 (m, 1 H);
1.60 – 1.65 (m, 4 H); 2.28 (dd, J = 9.3, 7.9, 2 H); 4.05 (t,
J = 6.4, 2 H). 13C-NMR (100 MHz, CDCl3): 14.1; 14.2;
19.2; 20.0; 22.6; 25.9; 29.2; 29.5 (29); 29.6 (99); 31.9; 31.9;
32.1; 32.1; 38.9; 64.4; 174.2. EI-MS (70 eV): 382 (2, M+),
325 (3), 311 (5), 283 (3), 238 (8), 210 (3), 145 (100), 127
(19), 109 (20), 97 (32), 83 (44).
REFERENCES
[1] A. G. Gibbs, S. Rajpurohit, in ‘Insect Hydrocarbons’, Eds. G. J.
ꢀ
Blomquist and A. G. Bagneres, Cambridge University Press,
Cambridge, UK, New York, 2010, p. 100.
ꢀ
[2] G. J. Blomquist, A. G. Bagneres, ‘Insect Hydrocarbons: Biol-
ogy, Biochemistry, and Chemical Ecology’, Cambridge Univer-
sity Press, Cambridge, UK, New York, 2010.
ꢀ
[3] M. Trabalon, A. G. Bagneres, in ‘Insect Hydrocarbons’, Eds. G.
ꢀ
J. Blomquist and A. G. Bagneres, Cambridge University Press,
Cambridge, UK, New York, 2010, p. 344.
[4] G. J. Blomquist, in ‘Insect Hydrocarbons’, Eds. G. J. Blomquist
ꢀ
and A. G. Bagneres, Cambridge University Press, Cambridge,
UK, New York, 2010, p. 19.
[5] S. Schulz, G. Beccaloni, R. Nishida, Y. Roisin, R. I. Vane-
Wright, J. N. McNeil, Z. Naturforsch. C 1998, 53c, 107.
[6] J. S. Buckner, in ‘Insect Hydrocarbons’, Eds. G. J. Blomquist
ꢀ
and A. G. Bagneres, Cambridge University Press, Cambridge,
UK, New York, 2010, p. 187.
12-Bromododecan-1-ol (33). This compound was syn-
thesized according to the General Procedure for the
monobromination of diols using dodecane-1,12-diol (32,
8 g, 39.6 mmol) and (40 ml, 48% in H2O). Rf 0.40 (10:1
pentane/Et2O). Yield: 39% (4.0 g). 1H-NMR (400 MHz,
CDCl3): 1.27 (s, 16 H); 1.52 – 1.58 (m, 2 H); 1.85 (q,
J = 6.9, 2 H); 3.30 (t, J = 7.0, 2 H); 3.63 (t, J = 6.3, 2 H).
13C-NMR (100 MHz, CDCl3): 25.7; 28.1; 28.7; 29.3 (59);
32.7; 32.8; 34.0; 63.0. EI-MS (70 eV): 264 (1, M+), 246 (1),
218 (6), 190 (3), 176 (4), 162 (23), 48 (39), 137 (18), 125
(7), 111 (28), 97 (75), 83 (78), 69 (90), 55 (100), 41 (75).
14-Methylheptadecan-1-ol (34). This compound was
synthesized according to the procedure described for the
synthesis of 15 by using Mg turnings (766 mg, 31.9 mmol),
1-bromo-2-methylpentane (5.27 g, 31.9 mmol), and abs.
THF (16 ml). The formed 2-pentylmagensium bromide
(27) was coupled with 12-bromododecan-1-ol (32, 3.38 g,
12.7 mmol) under Li2CuCl4 (5 ml, 0.1M in THF) catalysis.
Rf 0.26 (3:1 pentane/Et2O). Yield: 21% (720 mg).1H-NMR
(400 MHz, CDCl3): 0.84 (d, J = 6.8, 3 H); 0.88 (t, J = 7.0, 3
H); 1.11 – 1.39 (m, 26 H); 1.41 – 1.48 (m, 1 H); 1.58 (quint.,
J = 6.7, 2 H); 3.4 (t, J = 7.1, 2 H). 13C-NMR (100 MHz,
CDCl3): 14.4; 19.6; 20.1; 25.7; 27.0; 29.6 (79); 30.0; 32.4;
32.8; 37.0; 39.4; 63.0. EI-MS (70 eV): 269 (1, M+), 252 (1),
224 (3), 209 (4), 181 (3), 168 (1), 153 (4), 139 (7), 125 (14),
111 (26), 97 (56), 84 (62), 69 (64), 55 (84), 43 (100).
[7] J. Takabayashi, S. Takahashi, Appl. Ent. Zool. 1986, 21, 114.
[8] S. Schulz, J. Chem. Ecol. 2013, 39, 1.
[9] L. Grinsted, T. Bilde, P. d’Ettorre, Behav. Ecol. 2011, 22, 1187.
[10] S. Schulz, in ‘Advances in Chemical Ecology, Advances in
ꢁ
Chemical Ecology’, Eds. R. T. Carde and J. G. Millar, Cam-
bridge University Press, Cambridge, 2004, p. 110; G. Uhl, D. O.
Elias, in ‘Spider behaviour’, Ed. M. E. Herberstein, Cambridge
Univ. Press, Cambridge, 2011, p. 127; A. C. Gaskett, Biol. Rev.
2007, 82, 26; B. A. Huber, Biol. Rev. 2005, 80, 363.
ꢀ
[11] M. Trabalon, A. G. Bagneres, N. Hartmann, A. M. Vallet,
Insect. Biochem. Mol. Biol. 1996, 26, 77.
[12] R. B. Suter, C. M. Shane, A. J. Hirscheimer, J. Arachnol. 1987,
15, 157.
[13] L. Baruffaldi, M. C. B. Andrade, Anim. Behav. 2015, 102, 25; M.
ꢀ
Trabalon, A. G. Bagneres, C. Roland, J. Chem. Ecol. 1997, 23, 747.
[14] A.-G. Bagneres, M. Trabalon, G. J. Blomquist, S. Schulz, Arch.
ꢀ
Insect. Biochem. Physiol. 1997, 36, 295.
[15] E. Provost, G. Riviere, M. Roux, A. G. Bagneres, J. L.
ꢀ
ꢁ
Clement, J. Chem. Ecol. 1994, 20, 2985.
[16] M. Trabalon, J. Insect. Physiol. 2011, 57, 735.
[17] S. Schulz, S. Toft, Tetrahedron 1993, 49, 6805.
[18] S. Schulz, Lipids 2001, 36, 637.
[19] S. Schulz, in ‘Bioorganic Chemistry – Highlights and New
Aspects’, Eds. U. Diederichsen, T. K. Lindhorst, B. Westermann
and L. A. Wessjohann, Wiley-VCH, Weinheim, 1999, p. 1.
[20] P. Sierwald, T. Fenzl, Florida Entomol. 1999, 82, 359.
[21] M. Whitehouse, in ‘Spider Behaviour’, Ed. M. E. Herberstein,
Cambridge Univ. Press, Cambridge, 2011, p. 348.
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