Reacción #2040

ord-2f15776952b34a539da4eb150087740b

Ecuación de reacción

C#CCC
1-butyne
CCCCC/C=C\CCCOC1CCCCO1
( 16 )
CCCCC/C=C\CCCOC1CCCCO1
(4Z)-1-(tetrahydropyran-2-yloxy)-4-decene
CC/C=C\C/C=C\CCCC#CCCOC1CCCCO1
( 6 )
CC/C=C\C/C=C\CCCC#CCCOC1CCCCO1
(8Z,11Z)-1-(tetrahydropyran-2-yloxy)-8,11-tetradecadien-3-yne
BrCCCCCCOC1CCCCO1
1-bromo-6-(tetrahydropyran-2-yloxy)-hexane
BrCCCCCCOC1CCCCO1
1-bromo-6-(tetrahydropyran-2-yloxy)hexane
BrCCCCCCOC1CCCCO1
1-bromo-6-(tetrahydropyran-2-yloxy)-hexane
CCCCC/C=C\CCCOC1CCCCO1
( 16 )
CCCCC/C=C\CCCOC1CCCCO1
(4Z)-1-(tetrahydropyran-2-yloxy)-4-decene
CCCCC/C=C\CCC/C=C/CCOC(C)=O
(3E,8Z)-3,8-tetradecadien-1-yl acetate
CC/C=C\C/C=C\CCC/C=C/CCOC(C)=O
( 9 )
CC/C=C\C/C=C\CCC/C=C/CCOC(C)=O
(3E,8Z,11Z)-3,8,11-tetradecatrien-1-yl acetate
CC/C=C\C/C=C\CCCCCCCO[Si](C)(C)C
( 12 )
CC/C=C\C/C=C\CCCCCCCO[Si](C)(C)C
(8Z,11Z)-trimethylsiloxy-8,11-tetradecadiene
CC/C=C\CCCCCC/C=C/CCOC(C)=O
(3E,11Z)-3,11-tetradecadien-1-yl acetate
Rendimiento 15.0%
CC/C=C\CCCCCC/C=C/CCOC(C)=O
(3E,11Z)-3,11-tetradecadienyl acetate
Rendimiento 15.0%

Disolventes

Condiciones de reacción

Condiciones detalladas
See reaction.notes.procedure_details.

Procedimiento

Starting from 1-butyne and 1-bromo-6-(tetrahydropyran-2-yloxy)-hexane (22), the (3E,11Z)-3,11-tetradecadien-1-yl acetate (30) was prepared by a synthetic route similar to that used for the preparation of (3E,8Z)-3,8-tetradecadien-1-yl acetate (21), as depicted in the following scheme. ##STR18## The yield was 15% [17 mg; 96% isomeric purity (GC)] based on the starting material, 1-bromo-6-(tetrahydropyran-2-yloxy)hexane (22). 1H NMR (500 MHz) δ: 5.51 (dtt, J=15.1, 6.8, 6.8, 1.2, 1.5 Hz, 1H, =CH -3), 5.35 (m, 3H, CH=CH -4, 11, 12), 4.06 (t, J=6.8, 6.8 Hz, 2H, CH2 -1), 2.31 (dddt, J=1.2, 1.2, 6.8, 6.8, 6.8 Hz, 2H, CH2 -2), 2.05 (s, 3H, COCH3), 2.02 (m, 6H, CH2 -5, 10, 13), 1.36-1.24 (m, 6H, CH2 -6, 7, 8, 9), 0.95 (t, J=7.3, 7.6 Hz, 3H, CH3). 13 C NMR (100.6 MHz) δ: 171.1 (C=O), 133.6 (=CH-3), 131.6 (=CH-12), 129.3 (=CH-11), 125.0 (=CH-4), 64.1 (CH2 -1), 32.6 (CH2 -2), 31.9 (CH2 -6), 29.7 (CH2 -8), 29.3 (CH2 -7), 29.1 (CH2 -9), 29.0 (CH2 -10), 27.1 (CH2 -5), 21.0 (COCH3), 20.5 (CH2 -13), 14.4 (CH3 -14). MS [EI, m/z(%)] 192 (M+ -60, 6), 163 (6), 149 (9), 135 (12), 121 (16), 107 (16), 96 (28), 95 (37), 93 (25), 82 (50), 81 (60), 80 (35), 79 (36), 69 (33) 68 (64), 67 (97), 55 (45), 43 (100), 41 (67). IR (CCl4, cm-1) 3006 (=CH cis str), 1743 (C=O), 1238, 1036 (C--O), 969 (=CH trans wag). IR (gas phase, cm-1) 3012 (cis =C--H str), 2934 (CH2), 1761 (C=O), 1231, 1038 (--O--), 968 (=CH trans wag).

Fuente

DOI: 10.6084/m9.figshare.5104873.v1Patente: US05728376uspto-grants-1998_03