Macroexpansionmethodology
3973
on column chromatography (silica gel, 0.5 × 5 cm, 5% ether in
pentane) gave 99.8mg (99.6%) of colorless crystals. Recrystal-
lization of this sample from cold pentane gave fine needles m.p.
53--54.5 ° (sealed capillary, lit. 52*. 53°).TM IR (CCI4): 2900, 2840,
1705, 1455, 1440, 1360era -~. NMR (CDCI3): 8 2.45 (t, 4H, J =
6 Hz), 2.2-1.2 (m, 22H). The mass spectrum was in accord with
the assigned structure. (Found: 210.19824. Calc. for CI4H260
1600, 1120, 1005, 990, 980, 960, 905 cm -J. NMR (CDCb): 6 9.6 (d,
IH, J = 7.5 Hz), 7.1-.4.9 (m, 7H), 2.7-1.0 (m, 10H). UVm~ 218 nm
(4.59). The mass spectrum of 20 was in accord with the assigned
structure. (Found: 206.13063) Calc. for Ct3Ht~Oz: 206.13067; Anal.
(Cl~HtsO2) C, H).
1,2-(E,E)-Di(I-buta-l,3-dienyl)cyclohexanol (21). To a 0° sus-
pension of metbyltriphenylphosphonium bromide (1.9g,
5.3 mmol) in 25 ml THF was added n-BuLl in hexane (2.21 ml,
4.8 mmol, 2.19M). The cooling bath was removed, the soln stirred
at room temp for 3 hr. and then cooled to -30°. Alcohol 20
(498.5 rag, 2.42 retool) in 6 ml THF was added dropwise to give a
light yellow suspension. After the addition was complete, the
suspension was stirred at - 300 for 45 rain, then warmed to room
temp for 45 rain. Pentane and NH4CI aq were added, and the
aqueous phase extracted with pentane. The combined extracts
were filtered and the solvent was removed in vacuo. Column
chromatography of the orange oil (silica gel, 2.5 x 10cm, 12%
ether in hexane) gave 378 mg (77%) of the title compound. IR
(CC14): 3600, 1650, 1600, 1005, 985, 955,905 cm- ~. NMR (CDCI~):
6.75--4.8 (m, 10H), 2.5 and 2.3 (m, IH, ratio 1: 10), I.%1.2 (m,
9H). UVm,, 220 nm (4.65). Mass spectrum of 21 was in accord
with the assigned structure. (Found: 204.15117. Calc. for
CvlH2oO: 204.15141). Anal. (Cl,,H2oO) C,H. CMR (CDCI3): ~5
141.8, 137.3, 136.7. 135.0, 132.4, 128.4, 116.5, 115.7, 73.1, 47.9,
38.0, 26.6, 25.3, 21.2.
210.19838)
A
2,4-DNP3°b-derivative
was obtained as
yellow/orange crystals, m.p. 117.5-118° (lit.z~" 117-118°).
Cyclotetradecanol. To
a 0° suspension of LAH (5.5rag,
0.14 mmol) in 0.5 ml ether was added cyclotetradecanone (7.6 rag,
0.036 retool) in I ml ether and the soln stirred for 40 rain. Stan-
dard workup gave 6.1 mg (79%) of a colorless solid, which on
recrystallization from pentane gave colorless granular crystals
m.p. 78.5-79.50 (lit/~c 78.6-79.4°).
(E),5-Hexadien-2-one (32). A mixture of anhyd SnCI4 (134.4g,
60ml, 0.516mol) and 400 ml CHrCI2 was cooled to -42° under
N:. A mixture of acetyl chloride (40.5g, 37ml, 0.516mol) and
300ml CHzCIz was added and the combined mixture stirred at
-42 °. Butadiene was slowly bubbled through the soln for l hr
and the mixture stirred an additional 0.5 hr at - 42°. The mixture
was allowed to warm to - 10¢ over I hr and was poured slowly
over ice containing 150ml 0.1 N HCI. The layers were separated
and the organic layer washed with 300ml water followed by
300 ml brine. The organic layer was dried (MgSO4) and solvent
was removed at reduced pressure. A mixture of anhyd CaCO3
(60g, 0.60 tool) and 100ml toluene was added to the residue and
the combined mixture stirred under N: at an oil bath temp of 85°
for 33 hr. Toluene was removed at reduced pressure. Distillation
of the resulting oil yielded 5.23 ~ of 32 contaminated with a trace
of toluene: b.p. 40-47° (10 ram). Flash chromatography on 6 in ×
50 mm silica using a 3: 1 hexane-ether mixture as eluant provided
4.30g (9%) of the title compound as a pale, yellow liquid; ~H
NMR (CDCh) 8 2.27 (s, 3H), 5.45-7.13 (m, 5H), ; IR (film) 1675,
1630, 1600cm-~.
Cyclotetradeca-3,5,7-trien-l-one (25). To a 0° suspension of
potassium hydride (404 rag, 2.2 retool, 22% in mineral oil) in 20 ml
of THF was added dropwise a soln of 21 (174.6 nag, 0.855 retool) in
4 ml THF. When the addition was complete, the soln was stirred
at 0° for 5rain, the cooling bath was removed, and the soln
allowed to warm to room temp for l hr. The soln was then
recooled to 0°, sat NH4CI aq added, and the aqueous phase
extracted with CH2CIz. The combined extracts were dried
(Na2SO4) and the solvent removed in vacuo. Column chromato-
graphy (silica gel, I x 14cm, 7% ether in hexane) gave 157.4mg
(90%) of the title compound as a faint yellow solid. Recrystal-
lization of this sample from cold pentane gave colorless needles,
m.p. 50.5-51.5¢. IR (CCh): 1705, 1650, 1440, 1430, I100, 990,
975cm-~. NMR (CDCh): ~ 6.2--4.75 (m, 6H), 3.1-2.75 (bd, 2H),
2.%2.3 (m, 2H), 2.3-1.8 (m, 6H), 1.75-1.25 (m, 4H). UV,na,
233nm (4.32). Mass spectrum of 25 was in accord with the
assigned structure. (Found: 204.15126. Calc. for Q4HzoO:
204.1541. Anal. (Cj4H2oO) C, H. CMR (CDCI3): 8 209.3, 134.2,
133.3 (2C), 131.2, 130.7, 125.4, 48.3, 42.6, 34.3, 32.7, 31.6,
26.4, 22.1.
5,8-Dimethyl-l,3(E),7(E and Z),9-decatetraen-5-ol (28). A mix-
ture of 3-methyl-l,4-pentadiene (3.185g, 0.039tool) and 8 ml dry
THF was stirred under N: and cooled to -78°. n-BuLl (9.2 ml,
0.022mol) in hexane was added dropwise by syringe, and the
soln allowed to warm to room temp over I hr. The dark orange
soln was stirred at room temp for I hr and was cooled to - 50°. A
mixture of 32 (1.715 g, 0.018 tool) and 8 ml dry TH F was added,
dropwise by syringe, and the soln stirred for 1.5 hr at -50° to
-30 °. The soln was allowed to warm to room temp and was
quenched with 10ml water. The layers were separated and the
aqueous layer was extracted with ether (3 x 25 ml). The combined
organic layers were dried (MgSO4) and solvent was removed at
reduced pressure. Flash chromatography on 6in × 90 mm silica
using 4:1 hexane--ether mixture as eluant provided 1.136g (36%)
of the title compound as a colorless liquid ( > 90% one isomerS4).
Rt = 0.35; 'H NMR (CDCI~) ~ 1.32 (s, 3H), 1.58 (s, IH), 1.77 (br,
s, 3H), 2.43 (d, J=7.7Hz, 2H), 4.1--6.59 (m, 9H); '3C NMR
(CD3OD) 6 12.2, 27.6, 42.4, 73.8, 111.2, 116.8, 129.1, 129.5, 137.2,
138.2, 141.9, 142.9 with minor intensities sppearing at ,5 30.8, 41.4,
and 112.5; IR (film) 3400, 2980, 1645, 1610, 1360, 1010, 990,
900cm-~; mass spectrum, role (%) 152 (18), 98 (100), 97 (82), 79
(50), 67 (47). (Found: C, 80.56; H, 10.16. Calc. for Ca2H~O: C,
80.84; H, 10.18).
Hal[-li[e determination ,for 21--,25. Alcohol 21 (48rag,
0.23 mmol) and biphenyl (internal standard, 11.3 rag, 0.07 mmole)
in 2 ml THF were cooled to 0° and transferred to a flask contain-
ing excess KH free from mineral oil. The mixture was main-
tained at 0° with the aid of an ice bath.
Aliquots of the mixture were removed at intervals, quenched
with NH4CI aq, dried (Na2SO4), and the resulting sample
analyzed by GC (20-ft x 0.125-in. 3% SE-30, column temp 160°,
flame ionization detection) to yield the following information:
RXN. time (rain) % 21 remaining half life (rain)
9-Methyl-4(E),8(E and Z),lO-undecatrien-2-one (31). A mixture
of KH (0.139g, 22.9% in mineral oil, 0.80retool) and 5ml dry
THF was stirred under N2 at room temp. To this mixture, a soln
of 28 (0.074 g, 0.41 retool) and 5 ml dry THF was added, at once,
by syringe. The soln was stirred for I hr at room temp and 10 ml
sat (NH4hSO4 aq was slowly added. The layers were separated
and the aqueous layer extracted with ether (3x 25 ml). The
combined organic layers were dried (MgSO,) and solvent was
removed under reduced pressure. The residue was submitted to
preparative tic (silica) using a mixture of 2:1 hexane--ether as
eluant. The product was isolated by CH.,CI2 extraction and
solvent removal under reduced pressure to provide 0.057 g (78%)
of the title compound ( > 90% one isomer~) as a clear, colorless
liquid; TH NMR (CDCh) 1.74 (br s, 3H), 2.13 (s, 3H), 2.16 (br s,
0
30
60
120
180
270
100
71
45
21
8
--
60.9
51.9
52.5
50.1
57.1
4
Cyclotetradecanone.
A room temp mixture of 25 (97.3mg,
0.476mmol) and 5% Pd-C (30rag) in 10ml EtOAc was flushed
first with Hz and then maintained under one atmosphere of H2
for 2 hr. Filtration of the mixture through celite with ether and
concentration in vacuo gave 114.9mg of colorless crystals which
Wender, Paul A.
