P. Kraft, W. Eichenberger
FULL PAPER
[C5H11ϩ], 57 (85) [C4H9ϩ]. Odor: Musky, slightly fruity-floral. 111 (100) [C8H15ϩ], 95 (16) [C7H11ϩ], 71 (66) [C4H7Oϩ], 69 (39)
ϩ
Odor threshold: 0.87 ng/L air.
[C8H14 Ϫ C3H5], 55 (29) [C4H7ϩ], 43 (41) [C3H7ϩ]. Odor:
Fruity, musky.
(2ЈЈE)-2Ј-Methyl-2Ј-(1ЈЈ,4ЈЈ,4ЈЈ-trimethylpent-2ЈЈ-enyloxy)propyl
Propionate (31): Following the procedure for the preparation of
1Ј,4Ј,4Ј-Trimethylpent-2-enyl (2ЈE)-4-Oxopentanoate (34): Steglich
8, (3E)-5,5-dimethylhex-3-en-2-ol (29.4 g, 229 mmol) was etherified esterification
of
(3E)-5,5-dimethylhex-3-en-2-ol
(760 mg,
with isobutylene oxide (19.8 g, 275 mmol) to provide, after FC (sil- 5.93 mmol) with 4-oxopentanoic acid (690 mg, 5.93 mmol) pro-
ica gel; pentane/Et2O, 9:1; Rf ϭ 0.27), 2-methyl-2-(1Ј,4Ј,4Ј-trimeth- vided, after the usual workup and purification by FC (silica gel;
ylpent-2Ј-enyloxy)propan-1-ol (4.21 g, 8%). According to the syn- pentane/Et2O, 9:1; Rf ϭ 0.14), the odoriferous title compound
thesis of 17, Steglich esterification of 2-methyl-2-(1Ј,4Ј,4Ј-trimethyl-
(1.21 g, 90%). IR (ATR): ν˜ ϭ 1721 (s, νCϭO), 1159 (s, νCϪO)
1
pent-2Ј-enyloxy)propan-1-ol (1.30 g, 6.49 mmol) with propionic cmϪ1. H NMR (CDCl3): δ ϭ 1.00 (s, 9 H, 4Ј-Me3), 1.28 (d, J ϭ
acid (480 mg, 6.49 mmol) and FC (silica gel; pentane/Et2O, 19:1;
Rf ϭ 0.14) furnished the odoriferous title compound (1.37 g, 82%).
6.0 Hz, 3 H, 1Ј-Me), 2.19 (s, 3 H, 5-H3), 2.56 (t, J ϭ 7.0 Hz, 2 H,
2-H2), 2.74 (td, J ϭ 7.0, 2.5 Hz, 2 H, 3-H2), 5.28Ϫ5.38 (m, 2 H,
1Ј-,2Ј-H), 5.69 (d, J ϭ 14.5 Hz, 1 H, 3Ј-H) ppm. 13C NMR
IR (ATR): ν˜ ϭ 1169/1063 (s, νCϪO), 1741 (s, νOϪCϭO) cmϪ1
.
1H NMR (CDCl3): δ ϭ 0.99 (s, 9 H, 4ЈЈ-Me3), 1.16 (t, J ϭ 7.0 Hz, (CDCl3): δ ϭ 20.4 (q, 1Ј-Me), 28.4 (t, C-2), 29.3 (3 q, 4Ј-Me3), 29.8
3 H, 3-H3), 1.17 (d, J ϭ 6.5 Hz, 3 H, 1ЈЈ-Me), 1.19 (s, 6 H, 2Ј-
(q, C-5), 32.7 (s, C-4), 37.9 (t, C-3), 71.6 (d, C-1Ј), 124.2 (d, C-2Ј),
Me2), 2.37 (q, J ϭ 7.0 Hz, 2 H, 2-H2), 3.94 (d, J ϭ 11.0 Hz, 1 H, 143.9 (d, C-3Ј), 171.9 (s, C-1), 206.6 (s, C-4) ppm. MS (70 eV):
1Ј-Hb), 4.00 (d, J ϭ 11.0 Hz, 1 H, 1Ј-Ha), 4.14 (quint. d, J ϭ 6.5,
1.0 Hz, 1 H, 1ЈЈ-H), 5.34 (dd, J ϭ 15.5, 6.5 Hz, 1 H, 2ЈЈ-H), 5.54
(dd, J ϭ 15.5, 1.0 Hz, 1 H, 3ЈЈ-H) ppm. 13C NMR (CDCl3): δ ϭ
m/z ϭ 208 (1) [Mϩ Ϫ H2O], 170 (5) [Mϩ Ϫ C4H8], 152 (1) [Mϩ
Ϫ
C4H8 Ϫ H2O], 127 (11) [C8H15Oϩ], 110 (16) [C8H15ϩ], 99 (100)
ϩ
ϩ
[C5H7O2ϩ], 95 (55) [C8H15 Ϫ CH3], 81 (9) [C5H7O2 Ϫ H2O], 67
9.09 (q, C-3), 23.8/23.9/23.9 (3 q, 2Ј-,1ЈЈ-Me), 27.6 (t, C-2), 29.4 (3 (25) [C5H7ϩ], 55 (30) [C4H7ϩ], 43 (37) [C2H3Oϩ]. Odor: Musky,
q, 4ЈЈ-Me3), 32.5 (s, C-4ЈЈ), 69.1 (d, C-1ЈЈ), 69.8 (t, C-1Ј), 74.4 (s,
C-2Ј), 129.3 (d, C-2ЈЈ), 140.3 (d, C-3ЈЈ), 174.2 (s, C-1) ppm. MS
(70 eV): m/z ϭ 241 (1) [Mϩ Ϫ CH3], 129 (20) [C8H17Oϩ], 127 (9)
fruity, pear, ambrette seed oil.
(2ЈЈE)-2Ј-(1ЈЈ,4ЈЈ-Dimethylpent-2ЈЈ-enyloxy)-2Ј-methylpropyl Propi-
onate (35): Following the procedure for the preparation of 8, (3E)-
5-dimethylhex-3-en-2-ol (108 g, 946 mmol) was etherified with iso-
butylene oxide (81.8 g, 1.14 mmol) to provide, after FC (silica gel;
[C8H15Oϩ], 111 (100) [C8H15ϩ], 95 (16) [C7H11ϩ], 69 (43) [C8H14
ϩ
Ϫ C3H5], 57 (92) [C4H9ϩ]. Odor: Green, grapefruit, slightly musky.
(2ЈЈE)-2Ј-Methyl-2Ј-(1ЈЈ,4ЈЈ,4ЈЈ-trimethylpent-2ЈЈ-enyloxy)propyl pentane/Et2O, 9:1; Rf ϭ 0.17), 2-methyl-2-(1Ј,4Ј-dimethylpent-2Ј-
Cyclopropanecarboxylate (32): According to the synthesis of 17, enyloxy)propan-1-ol (24.8 g, 14%). Steglich esterification of 2-
Steglich esterification of 2-methyl-2-(1Ј,4Ј,4Ј-trimethylpent-2Ј-en- methyl-2-(1Ј,4Ј-dimethylpent-2Ј-enyloxy)propan-1-ol (1.80 g, 9.66
yloxy)propan-1-ol (1.30 g, 6.49 mmol) with cyclopropanecar- mmol) with propionic acid (1.19 g, 16.1 mmol) and the usual
boxylic acid (590 mg, 6.49 mmol) and FC (silica gel; pentane/Et2O,
workup with FC (silica gel; pentane/Et2O, 19:1; Rf ϭ 0.31) fur-
19:1; Rf ϭ 0.29) furnished the odoriferous title compound (1.46 g,
nished the odoriferous title compound (1.00 g, 43%). IR (ATR):
84%). IR (ATR): ν˜ ϭ 1163/1063 cmϪ1 (s, νCϪO), 1731 cmϪ1 (s, ν˜ ϭ 1168/1057 (s, νCϪO), 1741 (s, νOϪCϭO) cmϪ1
.
1H NMR
1
νOϪCϭO). H NMR (CDCl3): δ ϭ 0.86 (mc, 2 H, 3-,4-Hb), 0.99 (CDCl3): δ ϭ 0.96/0.97 (2 d, J ϭ 7.0 Hz, 6 H, 4ЈЈ-Me2), 1.16 (t,
(s, 9 H, 4ЈЈ-Me3), 1.02 (mc, 2 H, 3-,4-Ha), 1.17 (d, J ϭ 6.5 Hz, 3 J ϭ 7.5 Hz, 3 H, 3-H3), 1.17 (d, J ϭ 6.5 Hz, 3 H, 1ЈЈ-Me), 1.20 (s,
H, 1ЈЈ-Me), 1.20 (s, 6 H, 2Ј-Me2), 1.66 (mc, 1 H, 2-H), 3.93 (d, J ϭ 6 H, 2Ј-Me2), 2.24 (br. oct., J ϭ 7.0 Hz, 1 H, 4ЈЈ-H), 2.37 (q, J ϭ
11.5 Hz, 1 H, 1Ј-Hb), 3.99 (d, J ϭ 11.5 Hz, 1 H, 1Ј-Ha), 4.13 (quint.
d, J ϭ 6.5, 1.0 Hz, 1 H, 1ЈЈ-H), 5.35 (dd, J ϭ 15.5, 6.5 Hz, 1 H,
7.5 Hz, 2 H, 2-H2), 3.95 (d, J ϭ 11.5 Hz, 1 H, 1Ј-Hb), 3.99 (d, J ϭ
11.5 Hz, 1 H, 1Ј-Ha), 4.12 (br. quint., J ϭ 6.5 Hz, 1 H, 1ЈЈ-H), 5.38
2ЈЈ-H), 5.54 (dd, J ϭ 15.5, 1.0 Hz, 1 H, 3ЈЈ-H) ppm. 13C NMR (ddd, J ϭ 15.5, 6.5, 1.0 Hz, 1 H, 2ЈЈ-H), 5.50 (ddd, J ϭ 15.5, 6.5,
(CDCl3): δ ϭ 8.33 (2 t, C-3,-4), 12.9 (d, C-2), 23.9/23.9/24.0 (3 q, 1.0 Hz, 1 H, 3ЈЈ-H) ppm. 13C NMR (CDCl3): δ ϭ 9.09 (q, C-3),
2Ј-,1ЈЈ-Me), 29.4 (3 q, 4ЈЈ-Me3), 32.5 (s, C-4ЈЈ), 69.1 (d, C-1ЈЈ), 69.8
21.2/22.2 (2 q, 4ЈЈ-Me), 23.7/23.8/23.9 (3 q, 2Ј-,1ЈЈ-Me), 27.6 (t, C-
(t, C-1Ј), 74.4 (s, C-2Ј), 129.3 (d, C-2ЈЈ), 140.3 (d, C-3ЈЈ), 174.6 (s, 2), 30.5 (d, C-4ЈЈ), 68.8 (d, C-1ЈЈ), 69.7 (t, C-1Ј), 74.4 (s, C-2Ј), 131.5
C-1) ppm. MS (70 eV): m/z ϭ 253 (1) [Mϩ Ϫ CH3], 141 (13) (d, C-2ЈЈ), 136.4 (d, C-3ЈЈ), 174.2 (s, C-1) ppm. MS (70 eV): m/z ϭ
[C8H13O2ϩ], 127 (9) [C8H15Oϩ], 111 (78) [C8H15ϩ], 95 (14) 227 (1) [Mϩ Ϫ CH3], 146 (1) [C7H14O3ϩ], 129 (15) [C8H17Oϩ], 113
[C7H11ϩ], 69 (100) [C8H14 Ϫ C3H5], 41 (33) [C3H5ϩ]. Odor: Fru-
(8) [C7H13Oϩ], 97 (100) [C7H13ϩ], 57 (80) [C4H9ϩ], 55 (56) [C7H13
ϩ
ϩ
ity, musky, powdery, anisic.
Ϫ C3H6]. Odor: Earthy, green, slightly musky.
(2ЈЈE)-2Ј-Methyl-2Ј-(1ЈЈ,4ЈЈ,4ЈЈ-trimethylpent-2ЈЈ-enyloxy)propyl Bu-
tyrate (33): According to the synthesis of 17, Steglich esterification
(2ЈЈE)-2Ј-(1ЈЈ,4ЈЈ-Dimethylpent-2ЈЈ-enyloxy)-2Ј-methylpropyl Cyclo-
propanecarboxylate (36): Steglich esterification of 2-methyl-2-(1Ј,4Ј-
of 2-methyl-2-(1Ј,4Ј,4Ј-trimethylpent-2Ј-enyloxy)propan-1-ol (1.30 g, dimethylpent-2Ј-enyloxy)propan-1-ol (1.80 g, 9.66 mmol) with
6.49 mmol) with butyric acid (570 mg, 6.49 mmol) and FC (silica
cyclopropanecarboxylic acid (1.40 g, 16.1 mmol) and the usual
gel; pentane/Et2O, 19:1; Rf ϭ 0.26) furnished the odoriferous title
workup with FC (silica gel; pentane/Et2O, 19:1; Rf ϭ 0.28) pro-
compound (1.45 g, 83%). IR (ATR): ν˜ ϭ 1168/1062 (s, νCϪO), vided the odoriferous title compound (900 mg, 37%). IR (ATR):
1738 (s, νOϪCϭO) cmϪ1 1H NMR (CDCl3): δ ϭ 0.96 (t, J ϭ ν˜ ϭ 1162 (s, νCϪO), 1730 (s, νOϪCϭO) cmϪ1. 1H NMR (CDCl3):
.
7.5 Hz, 3 H, 4-H3), 0.99 (s, 9 H, 4ЈЈ-Me3), 1.16 (d, J ϭ 6.5 Hz, 3 δ ϭ 0.86 (mc, 2 H, 3-,4-Hb), 0.96/0.97 (2 d, J ϭ 7.0 Hz, 6 H, 4ЈЈ-
H, 1ЈЈ-Me), 1.20 (s, 6 H, 2Ј-Me2), 1.68 (sext, J ϭ 7.5 Hz, 2 H, 3- Me2), 1.02 (mc, 2 H, 3-,4-Ha), 1.17 (d, J ϭ 6.5 Hz, 3 H, 1ЈЈ-Me),
H2), 2.33 (t, J ϭ 7.5 Hz, 2 H, 2-H2), 3.94 (d, J ϭ 11.5 Hz, 1 H, 1Ј- 1.21 (s, 6 H, 2Ј-Me2), 1.65 (mc, 1 H, 2-H), 2.24 (br. oct., J ϭ 7.0 Hz,
Hb), 4.02 (d, J ϭ 11.0 Hz, 1 H, 1Ј-Ha), 4.13 (quint. d, J ϭ 6.5,
1 H, 4ЈЈ-H), 3.94 (d, J ϭ 11.0 Hz, 1 H, 1Ј-Hb), 3.98 (d, J ϭ 11.0 Hz,
1.0 Hz, 1 H, 1ЈЈ-H), 5.35 (dd, J ϭ 15.5, 6.5 Hz, 1 H, 2ЈЈ-H), 5.54 1 H, 1Ј-Ha), 4.12 (br. quint., J ϭ 6.5 Hz, 1 H, 1ЈЈ-H), 5.39 (ddd,
(dd, J ϭ 15.5, 1.0 Hz, 1 H, 3ЈЈ-H) ppm. 13C NMR (CDCl3): δ ϭ J ϭ 15.5, 6.5, 1.0 Hz, 1 H, 2ЈЈ-H), 5.51 (ddd, J ϭ 15.5, 6.5, 1.0 Hz,
13.7 (q, C-4), 18.4 (t, C-3), 23.8/23.9/24.0 (3 q, 2Ј-,1ЈЈ-Me), 29.4 (3
1 H, 3ЈЈ-H) ppm. 13C NMR (CDCl3): δ ϭ 8.29/8.30 (2 t, C-3,-4),
q, 4ЈЈ-Me3), 32.5 (s, C-4ЈЈ), 36.2 (t, C-2), 69.1 (d, C-1ЈЈ), 69.7 (t, C- 12.9 (d, C-2), 22.1/22.2 (2 q, 4ЈЈ-Me2), 23.7/23.8/23.9 (3 q, 2Ј-,1ЈЈ-
1Ј), 74.4 (s, C-2Ј), 129.3 (d, C-2ЈЈ), 140.3 (d, C-3ЈЈ), 173.4 (s, C-1) Me), 30.5 (d, C-4ЈЈ), 68.8 (d, C-1ЈЈ), 69.7 (t, C-1Ј), 74.4 (s, C-2Ј),
ppm. MS (70 eV): m/z ϭ 143 (15) [C8H15O2ϩ], 127 (10) [C8H15Oϩ],
131.5 (d, C-2ЈЈ), 136.4 (d, C-3ЈЈ), 174.6 (s, C-1) ppm. MS (70 eV):
364
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2004, 354Ϫ365