A general and convenient synthesis of highly substituted conjugated trienynes

Article abstract of DOI:10.1055/s-2003-38078

A convenient synthesis of highly substituted, non-linear conjugated trienynes is described. Our strategy involves the reaction of readily available thiophosphates with sodium derivative of dienynes, in which new single and double carbon-carbon bonds are f

Full text of DOI:10.1055/s-2003-38078

PAPER
723
A General and Convenient Synthesis of Highly Substituted Conjugated
Trienynes
S
ynthesi
w
s
of
H
ighly Substi
o
tuted Conjug
n
a
ted Trienyn
a
e
s
Maci giewicz, Piotr Dybowski, Aleksandra Skowro ska*
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, 90-363 ód , Sienkiewicza 112, Poland
Fax +48(42)6847126; E-mail: askow@bilbo.cbmm.lodz.pl
Received 2 January 2003
Abstract: A convenient synthesis of highly substituted, non-linear
conjugated trienynes is described. Our strategy involves the reac-
tion of readily available thiophosphates with sodium derivative of
dienynes, in which new single and double carbon–carbon bonds are
formed.
Key words: thiophosphates, trienynes, acetylide anions, carbonyl
compounds
Highly unsaturated compounds are useful intermediates
in organic synthesis, in particular as attractive precursors
of conjugated polyenes.1 They also occur in a number
Scheme 1
of natural products.2 In past decades attention has been
devoted to the exploration of conjugated organic materi-
als and polymers as sources of advanced materials for
transformation of thiophosphates 1 into trienynes 9 is il-
lustrated in Scheme 2.
electronic and optical applications.3
Several synthesis of highly unsaturated compounds of dif-
ferent structures are known.4 It is surprising, however,
that only one synthesis of non-linear trienynes has been
reported. It involves dimerization of terminal alkynes pro-
moted by methylaluminoxane.5
Addition of enyne anions 5 to thiophosphates 1 provides
two diastereoisomeric anions 6. These intermediate an-
ions undergo a rearrangement involving migration of a
phosphoryl group from sulfur to oxygen affording thiolate
anions 7. Subsequent cyclization of 7 with elimination of
phosphate anion gives episulfides 8 which lose sulfur
spontaneously to provide trienynes 9 in good to moderate
yields. The results are shown in Table 1. The reaction de-
scribed is fully chemoselective. Nucleophilic attack pro-
ceeds exclusively on the carbon atom of the carbonyl
group. The reaction exhibits low olefin stereoselectivity,
but the stereochemistry of the starting thiophosphates and
enynes is preserved in the final products.
We have already described a strategy for the stereoselec-
tive conversion of carbonyl compounds into olefins. The
key intermediates in this methodology are thiophosphates
and their seleno analogues.6 Using this methodology, we
have already elaborated the synthesis of a number of ver-
satile and synthetically valuable unsaturated compounds7
including enynes8 and dienynes.9
Herein we report a general and simple synthesis of conju-
gated non-linear trienynes based on our methodology. The
thiophosphates 1 containing an α,β-unsaturated carbonyl
moiety are easily made from the corresponding carbonyl
compounds 2 in high yield.10 Formation of 1 proceeds via
initial conversion of carbonyl compounds 2 into O-silylat-
ed dienolates 3,11 followed by addition of the readily
available (EtO)2P(O)SCl (4)12 (Scheme 1).
Similar reaction between the corresponding anion (gener-
ated from dienyne using NaNH2 in THF) and thiophos-
phate 1 afforded the new polyenyne 10 (Figure 1) in 35%
yield.
The structures and stereochemistry of trienynes 9 and
1
polyenyne 10 have been confirmed by H NMR, 13C
NMR, NOESY, CH-correlation, MS, and IR spectrosco-
We have found that thiophosphates 1 react readily with
the sodium derivative of dienynes 5 (generated from di-
enynes with NaNH2 in THF at room temperature) to pro-
vide, in one operation via single and double carbon–
carbon bond formation, highly substituted conjugated
non-linear trienynes 9. The basic concept of a one-pot
Synthesis 2003, No. 5, Print: 01 04 2003.
Art Id.1437-210X,E;2003,0,05,0723,0727,ftx,en;Z00103SS.pdf.
© Georg Thieme Verlag Stuttgart · New York
ISSN 0039-7881
Figure 1 Structure of polyenyne 10

724
I. Maci giewicz et al.
Scheme 2
Then a sat. aq solution of NH4Cl (15 mL) was added and the mixture
was extracted with Et2O (3 × 30 mL). The organic layer was washed
with ice-water (4 × 100 mL), dried (MgSO4) and the crude trienyne
9 was purified by flash chromatography on silica gel using benzene
as eluent.
py. The configuration of dominating trienynes was estab-
lished as Z based on NOE difference experiments
(observed effect in the range of 5–10% on the proton
ArCH=CH on irradiation of
ArCH=CHC=CCH3R).
methyl
group
5-Benzylidenyl-6-methylhepta-1,5-diene-3-yne (9a)
Yield: 58%; light yellow oil; Rf 0.89 (benzene).
In conclusion, application of methodology based on inter-
mediate thiophosphates provides a general and conve-
nient route to a wide range of conjugated trienynes. Of
particular interest are the formation of new single and
double carbon–carbon bonds in a single reaction and the
possibility of introduction of different substituents into
trienyne structures. Application of these compounds to the
synthesis of cyclic systems is currently under investiga-
tion in our laboratory.
IR (neat): 2246 (br w, C≡C), 1617 (br m, C=C), 1667 (br w, C=C).
1H NMR (CDCl3, 500 MHz): δ = 2.028 and 2.14 [s, 3 H, (CH3)2C=],
2.03 [m = appr. br t, 3 H, J = <1 Hz, C≡C–C(CH3)], 5.27 [quin, 1 H,
J = 1.69 Hz, C≡C–C(CH3)=CHH, H trans to CH3], 5.38 [m = appr.
br d, 1 H, J = 0.93 Hz, C≡C–C(CH3)=CHH, H cis to CH3], 6.94 and
7.07 (d, 1 H each, Jtrans = 15.60 Hz, CH=CH), 7.22 (t, 1 H, J = 7.35
Hz, Harom, para), 7.33 (t, 2 H, J = 7.69 Hz, Harom, meta), 7.45 (d, 2
H, J = 7.59 Hz, Harom, ortho).
13C NMR (CDCl3, DRX 500): δ = 20.2, 23.8, 24.7, 24.8 (CH3), 85.6,
95.7 (C≡C), 117.5 (–C=), 120.8 (CH2=C), 124.3, 130.3 (CH=CH),
126.5, 127.2, 128.7 (CHarom), 127.2 (CH2=C), 137.8 (Carom, ipso),
143.7 (–C=).
All reactions and manipulations of acetylide materials were per-
formed under dry argon. Et2O and THF were distilled under argon
from Na/benzophenone directly into the reaction flask. NMR spec-
tra were recorded on Bruker AC 200 and Bruker DRX 500 spec-
trometers. Chemical shifts 1H NMR and 13C NMR are referenced to
internal solvent resonances and are reported in relation to tetrame-
thylsilane. MS experiments were conducted on a Finnigan MAT95
spectrometer.
MS/EI: m/z = 222.2 (M+), 207.1, 192.1, 178.1,165.1.
MS/CI (isobutane): m/z = 223.1 (M + 1).
HRMS/EI: m/z calcd for C17H18 222.1409; found 222.1401 (M+).
5-Benzylidenyl-6-methylnona-1,5-diene-3-yne (9b)
Trienynes 9 and 10; General Procedure
Yield: 50%; light yellow oil; isomer ratio = 64:36 (Z/E) (according
to 1H NMR spectroscopy); Rf 0.79 and 0.95 (benzene); GC (HP 50
+ 15M 50/2/260, 20/min): Rt 10.514 min/84.766% (both isomers).
A solution of SO2Cl2 (0.02 mol) in CH2Cl2 (10 mL) was added drop-
wise to a stirred solution of O,O,O-triethylsilyl phosphothioate
(0.02 mol) in CH2Cl2 (5 mL) at –5 °C and the stirring was continued
for 20 min at r.t. After removal of about 80% of the solvent in vac-
uo, the crude (EtO)2P(O)SCl obtained was added dropwise to a
stirred solution of freshly prepared (from the corresponding ketone
by the action of TMSCl, NaI, Et3N in MeCN at r.t.) O-silylated di-
enolate (0.021 mol) in CH2Cl2 (10 mL) at –78 °C. The stirring was
continued at r.t. for an additional 1–2 h. The solvent and trimethyl-
silyl chloride were removed under reduced pressure to give thio-
phosphate 1, which was purified by column chromatography on
silica gel, using benzene and then benzene–EtOAc (2:1) as eluent.
Then a solution of pure 1 (0.018 mol) in THF (10 mL) was added
dropwise to a stirred solution (or suspension) of acetylide derivative
5 (0.02 mol) generated from the appropriate acetylene compound in
THF (15 mL) with NaNH2 at r.t. (anion is obtained quantitatively
after stirring for 1–3 h). A little exothermic effect was observed and
the reaction mixture became yellow. The stirring was continued for
10 min, during which time the reaction mixture became brownish.
IR (film): 2960, 2930, 2871 (CH), 2250 (w, C≡C, major isomer),
2192 (br w, C≡C, minor isomer), 1612 (br m, C=C, major isomer),
1583 (w, double, C=C, minor isomer), 1449 (m), 956 (m), 909 (s),
734 (vs), 693 (m).
1H NMR (CDCl3, 500 MHz): δ (major isomer) = 0.974 (t, 3 H,
J = 7.39 Hz, CH3CH2CH2), 1.53 (sext, 2 H, J = ca. 7.50 Hz,
CH3CH2CH2), 2.13 (s, 3 H, CH3C=C–CH=), 2.03 [br t, 3 H, J = 1.49
Hz, CH2=C(CH3)–C≡C], 2.37 (dd, 2 H, J1 = 7.85 Hz, J2 = 6.34 Hz,
CH3CH2CH2), 5.27 [quin, 1 H, J = 1.82, C≡C–C(CH3)=CHH, H
trans to CH3], 5.38 (br quin, 1 H, J = 1.01 Hz, C≡C–C(CH3)=CHH),
6.96 (d, 1 H, Jtrans = 15.60 Hz, –CH=), 7.07 (d, 11 H, Jtrans = 15.60
Hz, –CH=), 7.23 (t, 1 H, J = 7.31 Hz, Harom, para), 7.33 (t, 2 H,
J = 7.48 Hz, Harom, meta), 7.44 (br d, 2 H, J = ca. 7.50 Hz, Harom
,
ortho). δ (minor isomer) = 0.970 (t, 3 H, J = 7.41 Hz, CH3CH2CH2),
1.55 (sext, 2 H, J = ca. 7.50 Hz, CH3CH2CH2), 2.01 (s, 3 H,
CH3C=C–CH=), 2.02 [br t, 3 H, J = 1.50 Hz, CH2=C(CH3)–C≡C],
Synthesis 2003, No. 5, 723–727 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Synthesis of Highly Substituted Conjugated Trienynes
725
Table 1 Preparation of Trienynes 9 from 1 and 5
9
Structure
Yielda (%)
IR (neat)b (cm–1)
13C NMRc δ
Z/E Ratiod
C=C
C≡C
C=C
C≡C
a
60
1667, 1617
2246
117.5, 143.7,
124.3, 130.3,
120.8, 127.2
85.6, 95.7
–
b
58
1612, 1583
2250, 2192
117.7, 147.7,
117.8, 147.8,
124.0, 130.3,
124.3, 130.5,
120.5, 120.6,
127.1, 128.2,
117.5, 148.3
85.6, 95.3,
85.8, 95.8
64:36e
c
d
e
53
45
56
1612, 1583
1612, 1583
2192
124.1, 130.3,
124.5, 130.4,
120.6, 120.7,
127.2, 128.3
58:42e
2183
114.5, 151.5,
123.7, 130.7,
120.7, 123.0
85.5, 95.5
–
1611, 1590,
1580
2258, 2192
118.1, 148.0,
118.2, 148.2,
120.6, 120.8f
85.8, 95.6,
86.0, 96.1
63:37e
f
41
40
1612
2193
2175
117.4, 140.8,
122.3, 139.6,
120.3, 129.5
95.1, 101.1
–
g
1633, 1600,
1571
118.3, 142.3,
118.3, 142.4,
119.6, 145.7,
119.9, 145.8,
124.5, 124.6,
130.3, 130.4
89.8, 95.5,
90.1, 95.8
50:50
a Based on thiophosphate, for analytically pure products.
b Neat.
c In CDCl3/TMS.
d According to 1H NMR spectroscopy.
e 1H NMR, NOE difference.
f CH=CH and CH2=C were superimposed with C-naphth.
2.49 (dd, 2 H, J1 = appr. J2 = ≤7.50 Hz, CH3CH2CH2), 5.26 [quin, 1
H, J = 1.68 Hz, C≡C–C(CH3)=CHH, H trans to CH3], 5.36 (br quin,
1 H, J = 0.96 Hz, C≡C–C(CH3)=CHH), 6.96 (d, 1 H, Jtrans = 15.60
Hz, –CH=), 7.06 (d, 1 H, Jtrans = 15.60 Hz, –CH=), 7.22 (t, 1 H,
J = 7.52 Hz, Harom, para), 7.32 (t, 2 H, J = 7.52 Hz, Harom, meta),
7.45 (br d, 2 H, J = ca. 7.50 Hz, Harom, ortho).
13C NMR (CDCl3, DRX 500): δ = 13.9 (minor) and 14.0 (major)
(CH2CH2CH3), 18.2 (CH3CH2, minor), 21.2 [CH3C(=CH2)–C≡C,
minor], 21.7 [CH3C(=CH2)–C≡C, major], 22.7 (CH3CH2, major),
23.6
[CH3CH2CH2C(CH3)=C,
minor],
23.6
[CH3CH2CH2C(CH3)=C, major), 35.8 (=CCH2, major), 40.3
(=CCH2, minor), 85.6 and 95.3 (C≡C, minor), 85.8 and 95.8 (C≡C),
117.7 (=C–, minor), 117.8 (=C–, major), 120.5 (=CH2, minor),
120.6 (=CH2, major), 124.0 (=CH–, major), 124.3 (=CH–, minor),
126.4, 127.1 and 128.4 (CHarom), 127.1, 128.2 (CH2=C), 130.3
(–CH=, major), 130.5 (–CH=, minor), 137.7, 137.7 (Carom),
147.7 (–C=, minor), 147.8 (–C=, major).
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726
I. Maci giewicz et al.
MS/EI: m/z = 250.1 (M+), 223.1, 207.1, 195.1, 181.1, 149.0, 105.0,
83.9, 77.0.
1H NMR (CDCl3, 500 MHz): δ = 0.88 [t, 0.6 × 3 H, J = 7.4
Hz, =C(Me)CH2CH2CH3], 0.90 [t, 0.4 × 3H, J = 7.4
Hz, =C(Me)CH2CH2CH3], 1.45 [sext, 0.6 × 2 H, J = 7.4
Hz, = C(Me)CH2CH2CH3], 1.49 [sext, 0.6 × 2 H, J = 7.4
Hz, =C(Me)CH2CH2CH3], 1.92 [s, 0.4 × 3 H, J = 7.4 Hz, =C(n-
Pr)CH3], 2.07 [s, 0.6 × 3 H, J = 7.4 Hz, =C(n-Pr)CH3], 1.98 [m = ca.
2 s, 3 H, CH2=CCH3], 2.29 [dd, 0.6 × 2 H, J1 = 7.8 Hz, J2 = 7.5
Hz, =C(Me)CH2CH2CH3], 2.43 [dd, 0.4 × 2 H, J1 = 7.8 Hz, J2 = 7.5
Hz, =C(Me)CH2CH2CH3], 5.20 (sext, ca. 1 H, J = ca. 1 Hz, CH2=C–
CH3), 5.31 (br s, 0.4 H, CH2=C–CH3), 5.33 (br s, 0.6 H, CH2=C–
CH3), 7.00 (d, 0.4 H, Jtrans = 15.1 Hz, CH=CH), 7.02 (d, 0.6 H,
MS/CI (isobutane): m/z = 251.2 (M + 1).
HRMS/EI: m/z calcd for C19H22 250.1722; found 250.1710 (M+).
2,6-Dimethyl-5-styryldodeca-1,5-diene-3-yne (9c)
Yield 53%; yellow oil; isomer ratio = 58:42 (Z/E) (according to 1H
NMR spectroscopy); Rf 0.91 (benzene); GC (HP 50 15m 50/2/260,
20/min): Rt 11.226 min/42.454% (Z); Rt 11.294 min/42.217% (E).
IR (neat): 3024 (m), 2955 (vs), 2927 (vs), 2858 (vs), 2192 (br w,
C≡C), 1612 (br m, C=C), 1583 (w, C=C), 1448 (br s), 955 (s), 891
(m), 795 (m), 751 (s), 692 (s).
Jtrans = 15.1 Hz, CH=CH), 7.42 (dd, 0.4 H, Jtrans = 15.1 Hz, ∆ν = 2
Hz, CH=CH), 7.39 (d, 0.6 H, Jtrans = 15.1 Hz, CH=CH), 7.32 (super-
imposed with 7.39) (m, 8 lines, 2 Harom), 7.55 (m = ca. 2 d, 2 H, J =
ca. 8.8 Hz, Harom), 7.66 (m, 4 lines, 2 Harom), 7.75 (d, 2 Harom, J = 8.9
Hz), 8.11 (m = ca. 2 d, 1 H, J = 8.9 Hz, Harom).
13C NMR (CDCl3, AC-200): δ = 14.0 (=CMeCH2CH2CH3), 18.2
(CH2=C–CH3], 21.3, 21.7 [=C(Me)CH2CH2CH3], 22.8, 23.7 [=C(n-
Pr)CH3], 35.8 and 40.3 [=C(Me)CH2CH2CH3], 85.8, 86.0 and 95.6,
96.1 (C≡C), 118.1, 118.2 (–C=), 120.6, 120.8 (CH2=C), 123.3,
123.7, 125.5, 125.7, 125.9, 126.9, 127.2, 127.4, 127.6, 128.2, 128.5
(CH of Ar, CH=CH and CH2C=), 131.3, 133.7, 135.4, 135.4 (Carom),
148.0, 148.2 (–C=).
1H NMR (CDCl3, 500 MHz): δ = 0.90 [t, 3 H, J = 7.6
Hz, =C(CH2)5CH3], 1.10–1.70 [mc, ca. 8 H, =CCH2(CH2)4CH3],
2.00 [s, 0.4 × 3 H, =C(n-Hex)CH3], 2.12 [s, 0.6 × 3 H, =C(n-
Hex)CH3], 2.01 (s, 0.4 × 3 H, CH2=CCH3), 2.02 (s, 0.6 × 3 H,
CH2=C–CH3), 2.38 (dd, 0.6 × 2H, J1 = 7.90 Hz, J2 = 7.78
Hz, =CCH2), 2.49 (dd, 0.4 × 2 H, J1 = 7.90 Hz, J2 = 7.76
Hz, =CCH2), 5.28 (br d, 0.6 × 2 H, J = ca. 1 Hz, CH2=C), 5.36, 5.38
(br s, ca. 0.2 × 2 H, CH2=C), 6.95 (d, 1 H, Jtrans = 15.6 Hz, CH=CH),
7.06 (d, 1 H, Jtrans = 15.6 Hz, ∆ν = 5.9 Hz, CH=CH), 7.20–7.45 (mc,
5 Harom).
13C NMR (CDCl3, AC-200, DEPT): δ = 14.0 [=C(CH2)5CH3], 18.3
[CH3C(=CH2)–C≡C], 22.5 [=C(CH2)4CH2CH3], 22.8, 23.7 [=C(n-
Hex)CH3], 27.6, 28.2, 31.7 [=C(Me)CH2CH2CH2CH2CH2CH3],
33.9, 38.3 [=C(Me)CH2], 85.8, 85.8 and 95.3, 95.9 (C≡C), 117.5
(–C=), 120.6, 120.7 (CH2=), 124.1, 124.5 and 130.3, 130.4
(CH=CH), 127.2, 128.3 (CH2C=), [126.5, 127.2, 128.5, CHarom],
137.8 (Carom), 148.3 (C=).
Anal. Calcd for C26H30: C, 91.17; H, 8.83. Found: C, 91.59; H, 8.44.
2,8-Dimethyl-5-isopropylidenenona-1,6-diene-3-yne (9f)
Yield: 41%; yellow needles; mp 31–31.5 °C (benzene–pentane); Rf
0.92 (benzene).
IR (neat): 2193 (w, C≡C), 1612 (br m, C=C).
1H NMR (CDCl3, 500 MHz): δ = 1.05 [d, 6 H, J = 6.8 Hz,
(CH3)2CH], 1.89 and 2.04 [s, 3 H, C(CH3)2], 1.97 (br s, 3 H,
CH2=C–CH3), 2.41 [oct, 1 H, J = ca. 6.8 Hz, (CH3)2CH], 5.21 (quin,
1 H, J = 1.2 Hz, CHH=C–CH3), 5.30 (q, 1 H, J = ca. 0.5 Hz,
CHH=C–CH3), 6.02 (dd, 1 H, Jtrans = 15.3 Hz, Jvic = 6.9 Hz,
CHCH=CH), 6.27 (dd, 1 H, Jtrans = 15.3 Hz, 4J = 1.0 Hz,
CHCH=CH).
MS/CI (isobutane): m/z = 293.3 (M + 1).
Anal. Calcd for C22H28: C, 90.35; H, 9.65. Found: C, 90.39; H, 9.78.
7-Phenyl-2-methyl-5-cyclohexylidenehepta-1,6-diene-3-yne
(9d)
Yield 45%; yellow oil; Rf 0.80–0.95 (benzene).
13C NMR (CDCl3, AC-200): δ = 21.7, 22.1, 22.6, 23.7, 24.4 (CH3),
95.1 and 101.1 (C≡C), 117.4 and 140.8 (C=C), 120.3 (CH2=C),
122.3 and 139.6 (C=C), 129.5 (CH2C=).
IR (neat): 2931 (vs), 2855 (s), 2183 (br w, C≡C), 1612 (m), 1583 (w,
double, C=C), 1447 (s), 1261 (s), 1101 (br s), 1016 (br s), 908 (vs),
795 (vs), 734 (vs), 694 (s).
1H NMR (CDCl3, 500 MHz): δ = [1.53 (m, 3 lines, 4 H), 1.57 (m, 2
H), 2.41 (m = appr. br quasi t, 2 H), 2.54 (m = approx. quasi t, 2 H),
CH2 ring], 1.93 (s, 3 H, CH2=CCH3), 5.17 (quint, ca. 1 H, J = ca. 1
Hz, CHH=CCH3), 5.27 (br s, w 1/2 = 5 Hz, CHH=CCH3), 6.89 (d,
1 H, Jtrans = 15.6 Hz, CH=CH), 7.05 (d, 1 H, Jtrans = 15.6 Hz,
CH=CH), 7.11 (t, 1 H, J = 7.36 Hz, C6H5), 7.21 (t, 2 H, J = 7.53 Hz,
C6H5), 7.34 (d, 2 H, J = 7.71 Hz, C6H5).
MS/CI (isobutane): m/z = 189.2 (M + 1).
1,6-Diphenyl-7-methyl-3-isopropylidenetrideca-1,6-diene-4-
yne (9g)
Yield: 40%; yellow mass; isomer ratio = 50:50 (according to H
1
NMR spectroscopy); Rf 0.88 (benzene–pentane, 1:1).
IR (neat): 2250 (w), 2175 (w, C≡C), 1633 (w), 1600 (m), 1571 (w,
13C NMR (CDCl3, AC-200): δ = 21.7 (CH2=CCH3), 26.6 (ring car-
bon in γ position to C=C), 28.0 (ring carbons in β positions to C=C),
30.4 and 34.8 (ring carbons in α positions to C=C), 85.5 and 95.5
(C≡C), 114.5 (–C=), 120.7 (CH2=C), 123.0 (CH2=C), 123.7 and
130.7 (CH=CH), [126.4, 127.1, 128.5 CHarom], 137.8 (Carom), 151.5
(–C=).
C=C).
1H NMR (CDCl3, 500 MHz): δ = 0.78 [m = appr. 2 br t, 3 H,
(CH2)5CH3], 1.10–1.54 [mc, 8 H, CH2(CH2)4CH3], 1.74 [s, 1.5
H, =C(n-Hex)CH3], 1.90 [s,
H, =C(CH3)2], 2.11 [s, 1.5 H, =C(n-Hex)CH3], 2.07 [dd, ca. 1 H,
J1 = 7.9 Hz, J2 = 7.8 Hz, CH2(CH2)4CH3], 2.53 [dd, ca. 1 H, J1 = 7.9
Hz, J2 = 7.7 Hz, CH2(CH2)4CH3], 6.79 and 6.97 (d, 1 H, Jtrans = 15.6
Hz, CH=CH), 7.07–7.36 (mc, 10 Harom).
3 H, =C(CH3)2], 2.00 [s, 3
MS/EI: m/z = 262.1 (M+), 233.1, 219.1, 205.1, 1179.0, 165.0, 141.0,
115.0, 91.0, 77.0.
13C NMR (CDCl3, DRX 500): δ = 14.1, 14.2 [(CH2)5CH3], 19.4,
20.2 [=C(n-Hex)CH3], 22.6, 22.7 (CH2CH2CH2CH2CH3), 24.7,
24.8 (CH2CH2CH2CH2CH3), 28.1, 28.3 (CH2CH2CH2CH2CH3),
31.6, 31.9, 32.0 (CH2CH2CH2CH2CH3), 34.4 and 38.0
[=C(Me)CH2], 29.2, 29.4, 29.5 [=C(CH3)2], 89.8, 90.1 and 95.5,
95.8 (C≡C), 118.3, 118.3 (–C=), 119.6, 119.9 (–C=), 124.5, 124.6
and 130.3, 130.4 (CH=CH), 126.4, 126.7, 127.1, 127.2, 128.0,
128.3, 128.5, 129.1, 129.3 (CHarom], 137.9, 140.2 (Carom), 142.3,
142.4 and 145.7, 145.8 (–C=).
HRMS/EI: m/z calcd for C20H22 262.1722; found 262.1714 (M+).
2,6-Dimethyl-5α-naphtylidenylnona-1,5-dieneyne (9e)
Yield 56%; yellow mass; isomer ratio = 63:37 (Z/E) (according to
1H NMR spectroscopy); Rf 0.88 (benzene).
IR (neat): 3058 (m), 2961 (s), 2930 (m), 2871 (m), 2258 (w, sharp),
2192 (br w, C≡C), 1611 (m), 1590 (w), 1580 (w, C=C), 908 (vs),
795 (vs), 776 (vs), 734 (vs).
Synthesis 2003, No. 5, 723–727 ISSN 0039-7881 © Thieme Stuttgart · New York

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Synthesis of Highly Substituted Conjugated Trienynes
727
Anal. Calcd for C29H34: C, 91.04; H, 8.96. Found: C, 90.39; H, 8.52.
References
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1-(2′,4′-Dichlorophenyl)-7-methyl-6-styryl-3-isopropylidenede-
ca-1,6-diene-4-yne (10)
Yield: 35%; yellow needles; mp 29–30 °C; isomer ratio = 50:50 (Z/
E) (according to 1H NMR spectroscopy); Rf 0.696 and 0.629 (ben-
zene–pentane, 1:1).
IR (neat): 2100 (w, C≡C), 1635 (w), 1609 (m), 1584 (m), 1550 (w,
C=C).
1H NMR (CDCl3, 500 MHz): δ (chemical shifts marked with an *
are from the 1H NMR spectrum measured in C6D6) = 0.88 (td, 3 H,
Jvic = 7.35 Hz, ∆ν = 20 Hz, CH2CH2CH3), (* 0.45 and 0.63) 1.45
(mc = appr. sext, 2 H, Jvic = ca. 7.4 Hz, CH2CH2CH3), (* 0.97 and
1.15) 1.76 [d, 6 H, ∆ν = 3.9 Hz, = C(CH3)2], (* 1.25 and 1.43) 1.90
[s, ca.1.5 H, =C(n-Pr)CH3], (* 1.33) 2.04 [s, ca.1.5 H, =C(n-
Pr)CH3], (* 1.76) 2.27 [dd,
1 H, J1 = 7.9 Hz, J2 = 7.5
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Hz, =C(CH3)CH2CH2CH3], (* 1.79) 2.41 [dd, 1 H, J1 = 7.9 Hz,
J2 = 7.5 Hz, =C(CH3)CH2CH2CH3], (* 2.19) 6.73 (* 6.38) and 6.91
(d, 1 H, Jtrans = 15.68 Hz, 2,4-Cl2C6H3CH=CH), 6.91 (d, 1 H,
Jtrans = 15.7 Hz, PhCH=CH), 6.96 (dd, 1 H, Jtrans = 15.7 Hz,
∆ν = 5.8 Hz, PhCH=CH), 7.10 (dd, 1 H, J1 = 8.4 Hz, ∆ν = 0.6 Hz,
2,4-Cl2C6H3, Harom β to C=C), 7.12 (t, 1 H, J = 6.2 Hz, C6H5), 7.23
(td, 2 H, J = 6.3 Hz, ∆ν = 2 Hz, C6H5), 7.28 (d, 1 H, J = 2.1 Hz,
ClCCHCCl), 7.35 (m, 5 lines, 2 H, C6H5), 7.40 (d, 1 H, J = 8.5 Hz,
2,4-diCl2C6H3, Harom α to C=C).
13C NMR (CDCl3, DRX 500): δ = 14.0 and 14.1 (CH2CH2CH3),
18.2, 18.3, 18.7 [=C(CH3)2 and isomer 1, =C(n-Pr)CH3], 22.8 [iso-
mer 2, =C(n-Pr)CH3], 35.8 and 40.2 [=C(CH3)CH2CH2CH3], 80.6,
80.9 and 92.5, 94.0 (C≡C), 116.8, 117.0 (–C=), 121.8 and 123.0
(2,4-Cl2C6H3CH=CH), 123.8 and 124.3 (Ph CH=CH), 126.5, 128.5,
127.3 (CH, C6H5), 127.1 and 127.3 and 129.5, 129.5 (CH, 2,4-
Cl2C6H3), 130.4 and 130.6 (CH=CH), 132.8 and 133.7 (Carom),
134.5 (Carom), 149.0, 149.4, 149.6 (Cquart) (assigned on the basis 1H-
13C correlation).
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MS/CI (isobutane): m/z = 435.6, 436.6 (M + 1).
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Acknowledgments
This work was supported by the Polish State Committee for Scien-
tific Research (KBN) grant no 3 T09A 02915. We thank Sebastian
Olejniczak and Katarzyna Ganicz for conducting NOE experi-
ments.
(10) Dybowski, P.; Koprowski, M.; Maci giewicz, I.;
Skowro ska, A. Synthesis 1999, 844.
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(12) Skowro ska, A.; Dembiski, R.; Gwara, J.; Michalski, J.
Phosphorus Sulfur Relat. Elem. 1988, 39, 119; and
references cited therein.
Synthesis 2003, No. 5, 723–727 ISSN 0039-7881 © Thieme Stuttgart · New York