1-Butyne → (3E,11Z)-3,11-tetradecadienyl acetate

HRID 1944

Reaction equation

HRID 1944 reaction equation
C#CCC.BrCCCCCCOC1CCCCO1.[C:19]([O:22][CH2:23][CH2:24]/[CH:25]=[CH:26]/[CH2:27][CH2:28][CH2:29]/[CH:30]=[CH:31]\[CH2:32][CH2:33][CH2:34][CH2:35][CH3:36])(=[O:21])[CH3:20].O1CCCCC1OCCC#CCCC/C=C\C/C=C\CC.C(OCC/C=C/CCC/C=C\C/C=C\CC)(=O)C.C[Si](C)(C)OCCCCCCC/C=C\C/C=C\CC.O1CCCCC1OCCC/C=C\CCCCC>C(Cl)(Cl)(Cl)Cl>[C:19]([O:22][CH2:23][CH2:24]/[CH:25]=[CH:26]/[CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32]/[CH:33]=[CH:34]\[CH2:35][CH3:36])(=[O:21])[CH3:20]

Participants

9

Reactant 7

HCID 78461-ButyneHCID 1038602-[(6-bromohexyl)oxy]tetrahydro-2H-pyran2×HCID 9992319Tetradeca-3,8,11-trienyl acetate, (3E,8Z,11Z)-HCID 105387863E,8Z-Tetradecadienyl acetateHCID 10989926(8Z,11Z)-1-(tetrahydropyran-2-yloxy)-8,11-tetradecadien-3-yneHCID 67591886(4Z)-1-(tetrahydropyran-2-yloxy)-4-decene2×HCID 86752267(8Z,11Z)-trimethylsiloxy-8,11-tetradecadiene

Product 1

HCID 86752266(3E,11Z)-3,11-tetradecadienyl acetateYield 15%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

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).

Sources & evidence

ORD record
ord-2f15776952b34a539da4eb150087740b
Source dataset
uspto-grants-1998_03
Patent number
US05728376

Linked notes

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