反応 #2040

ord-2f15776952b34a539da4eb150087740b

反応方程式

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
収率 15.0%
CC/C=C\CCCCCC/C=C/CCOC(C)=O
(3E,11Z)-3,11-tetradecadienyl acetate
収率 15.0%

溶媒

反応条件

詳細条件
See reaction.notes.procedure_details.

実験手順

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).

出典

DOI: 10.6084/m9.figshare.5104873.v1特許: US05728376uspto-grants-1998_03